Non-cementitious compositions comprising co2 sequestering additives

ABSTRACT

Non-cementitious CO 2  sequestering compositions are provided. The compositions of the invention include a CO 2  sequestering additive, e.g., a CO 2  sequestering carbonate composition. Additional aspects of the invention include methods of making and using the non-cementitious CO 2  sequestering compositions.

CROSS-REFERENCE

This application is a divisional of and claims the benefit of U.S.patent application Ser. No. 12/209,491, titled “NON-CEMENTITIOUSCOMPOSITIONS COMPRISING CO₂ SEQUESTERING ADDITIVES”, filed 30 Oct. 2009,which in turn claims the benefit of: U.S. Provisional Application No.61/110,495, titled “NON-CEMENTITIOUS COMPOSITIONS COMPRISING CO₂SEQUESTERING ADDITIVES,” filed 31 Oct. 2008; U.S. ProvisionalApplication No. 61/149,949, titled “NON-CEMENTITIOUS COMPOSITIONSCOMPRISING CO₂ SEQUESTERING ADDITIVES,” filed 4 Feb. 2009; and U.S.Provisional Application No. 61/181,250, titled, “COMPOSITIONS ANDMETHODS USING SUBSTANCES WITH NEGATIVE DELTA13C VALUES,” filed 26 May2009, which applications are incorporated herein by reference.

BACKGROUND OF THE INVENTION

Carbon dioxide (CO₂) emissions have been identified as a majorcontributor to the phenomenon of global warming and ocean acidification.CO₂ is a by-product of combustion and it creates operational, economic,and environmental problems. It is expected that elevated atmosphericconcentrations of CO₂ and other greenhouse gases will facilitate greaterstorage of heat within the atmosphere leading to enhanced surfacetemperatures and rapid climate change. CO₂ has also been interactingwith the oceans driving down the pH toward 8.0. CO₂ monitoring has shownatmospheric CO₂ has risen from approximately 280 ppm in the 1950s toapproximately 380 pmm today, and is expect to exceed 400 ppm in the nextdecade. The impact of climate change will likely be economicallyexpensive and environmentally hazardous. Reducing potential risks ofclimate change will require sequestration of atmospheric CO₂.

SUMMARY OF THE INVENTION

In some embodiments, the invention provides a non-cementitiouscomposition that includes a CO₂ sequestering additive, in which the CO₂sequestering additive includes carbon that was released in the form ofCO₂ from the combustion of fuel. In some embodiments, the inventionprovides a non-cementitious composition in which the CO₂ sequesteringadditive is a carbonate compound. In some embodiments, the inventionprovides a non-cementitious composition in which the carbonate compoundcomposition includes a precipitate from analkaline-earth-metal-containing water. In some embodiments, theinvention provides a non-cementitious composition in which thealkaline-earth-metal-containing water from which the carbonate compoundcomposition precipitate forms includes CO₂ derived from an industrialwaste stream. In some embodiments, the invention provides anon-cementitious composition in which the non-cementitious compositionis a paper product. In some embodiments, the invention provides anon-cementitious composition in which the non-cementitious compositionis a polymeric product. In some embodiments, the invention provides anon-cementitious composition in which the non-cementitious compositionis a lubricant. In some embodiments, the invention provides anon-cementitious composition in which the non-cementitious compositionis an adhesive. In some embodiments, the invention provides anon-cementitious composition in which the non-cementitious compositionis rubber. In some embodiments, the invention provides anon-cementitious composition in which the non-cementitious compositionis chalk. In some embodiments, the invention provides a non-cementitiouscomposition in which the non-cementitious composition is an asphaltproduct. In some embodiments, the invention provides a non-cementitiouscomposition in which the non-cementitious composition is paint. In someembodiments, the invention provides a non-cementitious composition inwhich the non-cementitious composition is an abrasive for paint removal.In some embodiments, the invention provides a non-cementitiouscomposition in which the non-cementitious composition is a personal careproduct. In some embodiments, the invention provides a non-cementitiouscomposition that is a personal care product in which the personal careproduct is a cosmetic. In some embodiments, the invention provides anon-cementitious composition that is a personal care product in whichthe personal care product is a cleaning product. In some embodiments,the invention provides a non-cementitious composition that is a personalcare product in which the personal care product is a personal hygieneproduct. In some embodiments, the invention provides a non-cementitiouscomposition in which the non-cementitious composition is an ingestibleproduct. In some embodiments, the invention provides a non-cementitiouscomposition that is an ingestible product, in which the ingestibleproduct is a liquid. In some embodiments, the invention provides anon-cementitious composition that is an ingestible product, in which theingestible product is a solid. In some embodiments, the inventionprovides a non-cementitious composition that is an ingestible product,in which the ingestible product is an animal ingestible product. In someembodiments, the invention provides a non-cementitious composition inwhich the non-cementitious composition is an agricultural product. Insome embodiments, the invention provides a non-cementitious compositionthat is an agricultural product, in which the agricultural product is asoil amendment product. In some embodiments, the invention provides anon-cementitious composition that is an agricultural product, in whichthe agricultural product is a pesticide. In some embodiments, theinvention provides a non-cementitious composition in which thenon-cementitious composition is an environmental remediation product. Insome embodiments, the invention provides a non-cementitious compositionthat is an environmental remediation product in which the environmentalremediation product is forest soil restoration. In some embodiments, theinvention provides a non-cementitious composition that is anenvironmental remediation product in which the environmental remediationproduct is neutralization of over-acidified water.

In some embodiments, the invention provides a method of producing anon-cementitious composition, in which the method includes obtaining aCO₂ sequestering additive, in which the CO₂ sequestering additiveincludes carbon that was released in the form of CO₂ from the combustionof fuel and producing a non-cementitious composition that includes theCO₂ sequestering additive. In some embodiments, the invention provides amethod of producing a non-cementitious composition in which the CO₂sequestering additive is a carbonate compound composition. In someembodiments, the invention provides a method of producing anon-cementitious composition in which the carbonate compound compositionincludes a precipitate from an alkaline-earth-metal-containing water. Insome embodiments, the invention provides a method of producing anon-cementitious composition in which thealkaline-earth-metal-containing water includes CO₂ derived from anindustrial waste stream. In some embodiments, the invention provides amethod of producing a non-cementitious composition in which thenon-cementitious composition is a paper product. In some embodiments,the invention provides a method of producing a non-cementitiouscomposition in which the non-cementitious composition is a lubricant. Insome embodiments, the invention provides a method of producing anon-cementitious composition in which the non-cementitious compositionis an adhesive. In some embodiments, the invention provides a method ofproducing a non-cementitious composition in which the non-cementitiouscomposition is rubber. In some embodiments, the invention provides amethod of producing a non-cementitious composition in which thenon-cementitious composition is chalk. In some embodiments, theinvention provides a method of producing a non-cementitious compositionin which the non-cementitious composition is an asphalt product. In someembodiments, the invention provides a method of producing anon-cementitious composition in which the non-cementitious compositionis paint. In some embodiments, the invention provides a method ofproducing a non-cementitious composition in which the non-cementitiouscomposition is an abrasive for paint removal. In some embodiments, theinvention provides a method of producing a non-cementitious compositionin which the non-cementitious composition is a personal care product. Insome embodiments, the invention provides a method of producing anon-cementitious composition that is a personal care product, in whichthe personal care product is a cosmetic. In some embodiments, theinvention provides a method of producing a non-cementitious compositionthat is a personal care product, in which the personal care product is acleaning product. In some embodiments, the invention provides a methodof producing a non-cementitious composition that is a personal careproduct, in which the personal care product is a personal hygieneproduct. In some embodiments, the invention provides a method ofproducing a non-cementitious composition in which the non-cementitiouscomposition is an ingestible product. In some embodiments, the inventionprovides a method of producing a non-cementitious composition that is aningestible product, in which the ingestible product is a liquid. In someembodiments, the invention provides a method of producing anon-cementitious composition that is an ingestible product, in which theingestible product is a solid. In some embodiments, the inventionprovides a method of producing a non-cementitious composition in whichthe non-cementitious composition is an animal ingestible product. Insome embodiments, the invention provides a method of producing anon-cementitious composition in which the non-cementitious compositionis an agricultural product. In some embodiments, the invention providesa method of producing a non-cementitious composition that is anagricultural product, in which the agricultural product is a soilamendment product. In some embodiments, the invention provides a methodof producing a non-cementitious composition that is an agriculturalproduct, in which the agricultural product is a pesticide. In someembodiments, the invention provides a method of producing anon-cementitious composition in which the non-cementitious compositionis an environmental remediation product. In some embodiments, theinvention provides a method of producing a non-cementitious that is anenvironmental remediation product, in which environmental remediationproduct is forest soil restoration. In some embodiments, the inventionprovides a method of producing a non-cementitious that is anenvironmental remediation product, in which environmental remediationproduct is neutralization of over-acidified water.

In some embodiments, the invention provides a method of sequesteringcarbon dioxide that includes precipitating a CO₂ sequestering carbonatecompound composition from an alkaline-earth-metal-containing water, inwhich the carbonate compound composition includes carbon that wasreleased in the form of CO₂ from the combustion of fuel and producing aCO₂ sequestering additive comprising the carbonate compound compositionand producing a non-cementitious composition comprising the CO₂sequestering additive. In some embodiments, the invention provides amethod of sequestering carbon dioxide in which thealkaline-earth-metal-containing water is contacted to an industrialwaste stream prior to the precipitation step.

INCORPORATION BY REFERENCE

All publications, patents, and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each individual publication, patent, or patent application wasspecifically and individually indicated to be incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features of the invention are set forth with particularity inthe appended claims. A better understanding of the features andadvantages of the present invention will be obtained by reference to thefollowing detailed description that sets forth illustrative embodiments,in which the principles of the invention are utilized, and theaccompanying drawings of which:

FIG. 1 provides a schematic of a CO₂ sequestering additive productionprocess according to an embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Non-cementitious CO₂ sequestering compositions are provided. Thecompositions of the invention include a CO₂ sequestering additive, e.g.,a CO₂ sequestering carbonate composition. Additional aspects of theinvention include methods of making and using the non-cementitious CO₂sequestering compositions.

Before the present invention is described in greater detail, it is to beunderstood that this invention is not limited to particular embodimentsdescribed, as such may, of course, vary. It is also to be understoodthat the terminology used herein is for the purpose of describingparticular embodiments only, and is not intended to be limiting, sincethe scope of the present invention will be limited only by the appendedclaims.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimit of that range and any other stated or intervening value in thatstated range, is encompassed within the invention. The upper and lowerlimits of these smaller ranges may independently be included in thesmaller ranges and are also encompassed within the invention, subject toany specifically excluded limit in the stated range. Where the statedrange includes one or both of the limits, ranges excluding either orboth of those included limits are also included in the invention.

Certain ranges are presented herein with numerical values being precededby the term “about.” The term “about” is used herein to provide literalsupport for the exact number that it precedes, as well as a number thatis near to or approximately the number that the term precedes. Indetermining whether a number is near to or approximately a specificallyrecited number, the near or approximating unrecited number may be anumber which, in the context in which it is presented, provides thesubstantial equivalent of the specifically recited number.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, representativeillustrative methods and materials are now described.

All publications and patents cited in this specification are hereinincorporated by reference as if each individual publication or patentwere specifically and individually indicated to be incorporated byreference and are incorporated herein by reference to disclose anddescribe the methods and/or materials in connection with which thepublications are cited. The citation of any publication is for itsdisclosure prior to the filing date and should not be construed as anadmission that the present invention is not entitled to antedate suchpublication by virtue of prior invention. Further, the dates ofpublication provided may be different from the actual publication dateswhich may need to be independently confirmed.

It is noted that, as used herein and in the appended claims, thesingular forms “a,” “an,” and “the” include plural references unless thecontext clearly dictates otherwise. It is further noted that the claimsmay be drafted to exclude any optional element. As such, this statementis intended to serve as antecedent basis for use of such exclusiveterminology as “solely,” “only” and the like in connection with therecitation of claim elements, or use of a “negative” limitation.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentinvention. Any recited method can be carried out in the order of eventsrecited or in any other order which is logically possible.

In further describing the subject invention, embodiments of thenon-cementitious CO₂ sequestering compositions, as well as methods andsystems for their production, will be described first in greater detail.Next, examples of methods of using the CO₂ sequestering compositionswill be reviewed further.

Non-Cementitious CO₂ Sequestering Compositions

Non-cementitious CO₂ sequestering compositions are provided by theinvention. By “CO₂ sequestering composition” is meant that thecomposition contains carbon derived from a fuel used by humans, e.g.,carbon having a fossil fuel origin. For example, CO₂ sequesteringcompositions according to aspects of the present invention containcarbon that was released in the form of CO₂ from the combustion of fuel.In certain embodiments, the carbon sequestered in a CO₂ sequesteringcomposition is in the form of a carbonate compound. Therefore, incertain embodiments, CO₂ sequestering compositions according to aspectsof the subject invention contain carbonate compounds where at least partof the carbon in the carbonate compounds is derived from a fuel used byhumans, e.g., a fossil fuel. As such, production of compositions of theinvention results in the placement of CO₂ into a storage stable form,e.g., a stable component of a non-cementitious composition. Productionof the CO₂ sequestering compositions of the invention thus results inthe prevention of CO₂ gas from entering the atmosphere. The compositionsof the invention provide for storage of CO₂ in a manner such that CO₂sequestered (i.e., fixed) in the composition does not become part of theatmosphere. Compositions of the invention keep their sequestered CO₂fixed for substantially the useful life the composition, if not longer,without significant, if any, release of the CO₂ from the composition. Assuch, where the compositions are consumable compositions, the CO₂ fixedtherein remains fixed for the life of the consumable, if not longer.

CO₂ sequestering compositions of the invention include compositions thatcontain carbonates and/or bicarbonates, which may be in combination witha divalent cation such as calcium and/or magnesium, or with a monovalentcation such as sodium. The carbonates and/or bicarbonates may be insolution, in solid form, or a combination of solution and solid form,e.g., a slurry. The carbonates and/or bicarbonates may contain carbondioxide from a source of carbon dioxide; in some embodiments the carbondioxide originates from the burning of fossil fuel, and thus some (e.g.,at least 10, 50, 60, 70, 80, 90, 95%) or substantially all (e.g., atleast 99, 99.5, or 99.9%) of the carbon in the carbonates and/orbicarbonates is of fossil fuel origin, i.e., of plant origin. As isknown, carbon of plant origin has a different ratio of stable isotopes(¹³C and ¹²C) than carbon of inorganic origin, and thus the carbon inthe carbonates and/or bicarbonates, in some embodiments, has a δ¹³C ofless than, e.g., −10‰, or less than −15‰, or less than −20‰, or lessthan −35‰, or less than −30‰, or less than −35‰ as described in furtherdetail herein below.

Compositions of the invention include a CO₂ sequestering additive. CO₂sequestering additives are components that store a significant amount ofCO₂ in a storage stable format, such that CO₂ gas is not readilyproduced from the product and released into the atmosphere. In certainembodiments, the CO₂ sequestering additives can store 50 tons or more ofCO₂, such as 100 tons or more of CO₂, including 250 tons or more of CO₂,for instance 500 tons or more of CO₂, such as 750 tons or more of CO₂,including 900 tons or more of CO₂ for every 1000 tons of composition ofthe invention. In certain embodiments, the CO₂ sequestering additives ofthe compositions of the invention comprise about 5% or more of CO₂, suchas about 10% or more of CO₂, including about 25% or more of CO₂, forinstance about 50% or more of CO₂, such as about 75% or more of CO₂,including about 90% or more of CO₂, e.g., present as one or morecarbonate compounds.

The CO₂ sequestering additives of the invention may include one or morecarbonate compounds. The amount of carbonate in the CO₂ sequesteringadditive, as determined by coulometry using the protocol described incoulometric titration, may be 40% or higher, such as 70% or higher,including 80% or higher. In some embodiments, where the Mg source is amafic mineral (as described in U.S. Provisional Application Ser. No.61/079,790, incorporated by reference herein), or an ash (as describedin U.S. Provisional Application Ser. No. 61/073,319, incorporated hereinby reference), the resultant product may be a composition containingsilica as well as carbonate. In these embodiments, the carbonate contentof the product may be as low as 10%.

The carbonate compounds of the CO₂ sequestering additives may bemetastable carbonate compounds that are precipitated from a water, suchas a salt-water, as described in greater detail below. The carbonatecompound compositions of the invention include precipitated crystallineand/or amorphous carbonate compounds. Specific carbonate minerals ofinterest include, but are not limited to: calcium carbonate minerals,magnesium carbonate minerals and calcium magnesium carbonate minerals.Calcium carbonate minerals of interest include, but are not limited to:calcite (CaCO₃), aragonite (CaCO₃), vaterite (CaCO₃), ikaite(CaCO₃.6H₂O), and amorphous calcium carbonate (CaCO₃.nH₂O). Magnesiumcarbonate minerals of interest include, but are not limited to:magnesite (MgCO₃), barringtonite (MgCO₃.2H₂O), nesquehonite(MgCO₃.3H₂O), lanfordite (MgCO₃.5H₂O) and amorphous magnesium calciumcarbonate (MgCO₃.nH₂O). Calcium magnesium carbonate minerals of interestinclude, but are not limited to dolomite (CaMgCO₃), huntite(CaMg₃(CO₃)₄) and sergeevite (Ca₂Mg₁₁(CO₃)₁₃.H₂O). In certainembodiments, non-carbonate compounds like brucite (Mg(OH)₂) may alsoform in combination with the minerals listed above. As indicated above,the compounds of the carbonate compound compositions are metastablecarbonate compounds (and may include one or more metastable hydroxidecompounds) that are more stable in saltwater than in freshwater, suchthat upon contact with fresh water of any pH they dissolve andre-precipitate into other fresh water stable compounds, e.g., mineralssuch as low-Mg calcite.

The CO₂ sequestering additives of the invention are derived from, e.g.,precipitated from, a water (as described in greater detail below). Asthe CO₂ sequestering products are precipitated from a water, they mayinclude one or more additives that are present in the water from whichthey are derived. For example, where the water is salt water, the CO₂sequestering products may include one or more compounds found in thesalt water source. These compounds may be used to identify the solidprecipitations of the compositions that come from the salt water source,where these identifying components and the amounts thereof arecollectively referred to herein as a saltwater source identifier. Forexample, if the saltwater source is sea water, identifying compoundsthat may be present in the precipitated solids of the compositionsinclude, but are not limited to: chloride, sodium, sulfur, potassium,bromide, silicon, strontium and the like. Any such source-identifying or“marker” elements would generally be present in small amounts, e.g., inamounts of 20,000 ppm or less, such as amounts of 2000 ppm or less. Incertain embodiments, the “marker” compound is strontium, which may bepresent in the precipitated incorporated into the aragonite lattice, andmake up 10,000 ppm or less, ranging in certain embodiments from 3 to10,000 ppm, such as from 5 to 5000 ppm, including 5 to 1000 ppm, e.g., 5to 500 ppm, including 5 to 100 ppm. Another “marker” compound ofinterest is magnesium, which may be present in amounts of up to 20% molesubstitution for calcium in carbonate compounds. The saltwater sourceidentifier of the compositions may vary depending on the particularsaltwater source employed to produce the saltwater-derived carbonatecomposition. Also of interest are isotopic markers that identify thewater source.

Depending on the particular non-cementitious material or product, theamount of CO₂ sequestering additive that is present may vary. In someinstances, the amount of CO₂ sequestering additive ranges from 5 to 75%w/w, such as 5 to 50% w/w including 5 to 25% w/w and including 5 to 10%w/w.

The compositions of the invention may be viewed as low-carbon footprintcompositions. Low-carbon footprint compositions have a reduced carbonfootprint as compared to corresponding compositions that lack the CO₂sequestering additive (where “corresponding” herein means the identicalcomposition but for the presence of the CO₂ sequestering additive of theinvention). Using any convenient carbon footprint calculator, themagnitude of carbon footprint reduction of the compositions of theinvention as compared to corresponding compositions that lack the CO₂sequestering additive may be 5% or more, such as 10% or more, including25%, 50%, 75% or even 100% or more. In certain embodiments, thelow-carbon footprint compositions of the invention are carbon neutral,in that they have substantially no, if any, calculated carbon footprint,e.g., as determined using any convenient carbon footprint calculatorthat is relevant for a particular composition of interest. Carbonneutral compositions of the invention include those compositions thatexhibit a carbon footprint of 50 lbs CO₂/cu yd material or less, such as10 lbs CO₂/cu yd material or less, including 5 lbs CO₂/cu yd material orless, where in certain embodiments the carbon neutral compositions have0 or negative lbs CO₂/cu yd material, such as negative 1 or more, e.g.,negative 3 or more lbs CO₂/cu yd material. In some instances, the lowcarbon footprint compositions have a significantly negative carbonfootprint, e.g., −100 or more lbs CO₂/cu yd or less.

In certain embodiments compositions of the invention will contain carbonfrom fossil fuel; because of its fossil fuel origin, the carbon isotopicfractionation (δ¹³C) value of such compositions will be different fromthat of compositions containing inorganic carbon, e.g., limestone. As isknown in the art, the plants from which fossil fuels are derivedpreferentially utilize ¹²C over ¹³C, thus fractionating the carbonisotopes so that the value of their ratio differs from that in theatmosphere in general; this value, when compared to a standard value(PeeDee Belemnite, or PDB, standard), is termed the carbon isotopicfractionation (δ¹³C) value. δ¹³C values for coal are generally in therange −30 to −20‰ and δ¹³C values for methane may be as low as −20‰ to−40‰ or even −40‰ to −80‰. δ¹³C values for atmospheric CO₂ are −10‰ to−7‰, for limestone +3‰ to −3‰, and for marine bicarbonate, no. Even ifthe non-cementitious material contains some natural limestone, or othersource of C with a higher (less negative) δ¹³C value than fossil fuel,its δ¹³C value generally will still be negative and less than (morenegative than) values for limestone or atmospheric CO₂. In someembodiments, the non-cementitious material or product includes aCO₂-sequestering additive comprising carbonates, bicarbonates, or acombination thereof, in which the carbonates, bicarbonates, or acombination thereof have a carbon isotopic fractionation (δ¹³C) valueless than −5.00‰. Compositions of the invention thus includes anon-cementitious material or product with a δ¹³C less than −10‰, such asless than −12‰, −14‰, −16‰, −18‰, −20‰, −22‰, −24‰, −26‰, −28‰, or lessthan −30‰. In some embodiments the invention provides a non-cementitiousmaterial or product with a δ¹³C less than −10‰. In some embodiments theinvention provides a non-cementitious material or product with a δ¹³Cless than −14‰. In some embodiments the invention provides anon-cementitious material or product with a δ¹³C less than −18‰. In someembodiments the invention provides a non-cementitious material orproduct with a δ¹³C less than −20‰. In some embodiments the inventionprovides a non-cementitious material or product with a δ¹³C less than−24‰. In some embodiments the invention provides a non-cementitiousmaterial or product with a δ¹³C less than −28‰. In some embodiments theinvention provides a non-cementitious material or product with a δ¹³Cless than −30‰. In some embodiments the invention provides anon-cementitious material or product with a δ¹³C less than −32‰. In someembodiments the invention provides a non-cementitious material orproduct with a δ¹³C less than −34‰. Such a non-cementitious materials orproducts may be carbonate-containing materials or products, as describedabove, e.g., a non-cementitious material or product with that containsat least 10, 20, 30, 40, 50, 60, 70, 80, or 90% carbonate, e.g., atleast 50% carbonate w/w.

The relative carbon isotope composition (δ¹³C) value with units of ‰(per mil) is a measure of the ratio of the concentration of two stableisotopes of carbon, namely ¹²C and ¹³C, relative to a standard offossilized belemnite (the PDB standard).

δ¹³C‰=[(¹³C/¹²C_(sample)−¹³C/¹²C_(PDB standard))/(¹³C/¹²C_(PDB standard))]×1000

¹²C is preferentially taken up by plants during photosynthesis and inother biological processes that use inorganic carbon because of itslower mass. The lower mass of ¹²C allows for kinetically limitedreactions to proceed more efficiently than with ¹³C. Thus, materialsthat are derived from plant material, e.g., fossil fuels, have relativecarbon isotope composition values that are less than those derived frominorganic sources. The carbon dioxide in flue gas produced from burningfossil fuels reflects the relative carbon isotope composition values ofthe organic material that was fossilized. Table 1 lists relative carbonisotope composition value ranges for relevant carbon sources forcomparison.

Material incorporating carbon from burning fossil fuels reflects δ¹³Cvalues that are more like those of plant derived material, i.e. less,than that which incorporates carbon from atmospheric or non-plant marinesources. Verification that the material produced by a carbon dioxidesequestering process is composed of carbon from burning fossil fuels caninclude measuring the δ¹³C value of the resultant material andconfirming that it is not similar to the values for atmospheric carbondioxide, nor marine sources of carbon.

TABLE 1 Relative carbon isotope composition (δ¹³C) values for carbonsources of interest. Carbon Source δ¹³C Range [‰] δ¹³C Average value [‰]C3 Plants (most higher −23 to −33 −27 plants) C4 Plants (most tropical−9 to −16 −13 and marsh plants) Atmosphere −6 to −7 −6 Marine Carbonate(CO₃) −2 to +2 0 Marine Bicarbonate −3 to +1 −1 (HCO₃) Coal fromYallourn Seam −27.1 to −23.2 −25.5 in Australia¹ Coal from Dean Coal Bed−24.47 to −25.14 −24.805 in Kentucky, USA² ¹Holdgate, G. R. et al.,Global and Planetary Change, 65 (2009) pp. 89-103. ²Elswick, E. R. etal., Applied Geochemistry, 22 (2007) pp. 2065-2077.

In some embodiments the invention provides a method of characterizing acomposition comprising measuring its relative carbon isotope composition(δ¹³C) value. In some embodiments the composition is a composition thatcontains carbonates, e.g., magnesium and/or calcium carbonates. Anysuitable method may be used for measuring the δ¹³C value, such as massspectrometry or off-axis integrated-cavity output spectroscopy (off-axisICOS).

One difference between the carbon isotopes is in their mass. Anymass-discerning technique sensitive enough to measure the amounts ofcarbon we have can be used to find ratios of the ¹³C to ¹²C isotopeconcentrations. Mass spectrometry is commonly used to find δ¹³C values.Commercially available are bench-top off-axis integrated-cavity outputspectroscopy (off-axis ICOS) instruments that are able to determine δ¹³Cvalues as well. These values are obtained by the differences in theenergies in the carbon-oxygen double bonds made by the ¹²C and ¹³Cisotopes in carbon dioxide. The δ¹³C value of a carbonate precipitatefrom a carbon sequestration process serves as a fingerprint for a CO₂gas source, as the value will vary from source to source, but in mostcarbon sequestration cases δ¹³C will generally be in a range of −9‰ to−35‰.

In some embodiments the methods further include the measurement of theamount of carbon in the composition. Any suitable technique for themeasurement of carbon may be used, such as coulometry.

Precipitation material, which comprises one or more synthetic carbonatesderived from industrial CO₂, reflects the relative carbon isotopecomposition (δ¹³C) of the fossil fuel (e.g., coal, oil, natural gas, orflue gas) from which the industrial CO₂ (from combustion of the fossilfuel) was derived. The relative carbon isotope composition (δ¹³C) valuewith units of ‰ (per mille) is a measure of the ratio of theconcentration of two stable isotopes of carbon, namely ¹²C and ¹³C,relative to a standard of fossilized belemnite (the PDB standard).

δ¹³C‰=[(¹³C/¹²C_(sample)−¹³C/¹²C_(PDB standard))/(¹³C/¹²C_(PDB standard))]×1000

As such, the δ¹³C value of the CO₂ sequestering additive serves as afingerprint for a CO₂ gas source. The δ¹³C value may vary from source tosource (i.e., fossil fuel source), but the δ¹³C value for composition ofthe invention generally, but not necessarily, ranges between −9‰ to−35‰. In some embodiments, the δ¹³C value for the CO₂ sequesteringadditive is between −1‰ and −50‰, between −5‰ and −40‰, between −5‰ and−35‰, between −7‰ and −40‰, between −7‰ and −35‰, between −9‰ and −40‰,or between −9‰ and −35‰. In some embodiments, the δ¹³C value for the CO₂sequestering additive is less than (i.e., more negative than) −3‰, −5‰,−6‰, −7‰, −8‰, −9‰, −10‰, −11‰, −12‰, −13‰, −14‰, −15‰, −16‰, −17‰,−18‰, −19‰, −20‰, −21‰, −22‰, −23‰, −24‰, −25‰, −26‰, −27‰, −28‰, −29‰,−30‰, −31‰, −32‰, −33‰, −34‰, −35‰, −36‰, −37‰, −38‰, −39‰, −40‰, −41‰,−42‰, −43‰, −44‰, or −45‰, wherein the more negative the δ¹³C value, themore rich the synthetic carbonate-containing composition is in ¹²C. Anysuitable method may be used for measuring the δ¹³C value, methodsincluding, but no limited to, mass spectrometry or off-axisintegrated-cavity output spectroscopy (off-axis ICOS).

The compositions of the invention may vary greatly. By non-cementitiousis meant that the compositions are not settable compositions, e.g.,hydraulic cements. As such, the compositions are not dried compositionsthat, when combined with a setting fluid, such as water, set to producea solid product. Illustrative compositions according to certainembodiments of the invention are now reviewed further in greater detail.However, the below review of compositions is not limiting on theinvention, and is provided solely to further describe exemplaryembodiments of the invention.

Paper Products

The present invention includes novel formulations which incorporate theCO₂ sequestering composition into paper products. The term “paperproducts” is employed to refer to a thin material that is suitable foruse in one or more of writing upon, printing upon or packaging andincludes products commonly known as paper, card stock, and paperboard.Card stock is a type of paper that is thicker and more durable thanpaper but more flexible than paperboard (e.g., cardboard). Paperproducts of the invention are produced by pressing together moist fibers(e.g., cellulose, polymeric) in the form of a pulp composition and thendrying the pressed fibers to form sheets of varying thickness. Paperproducts of the invention may be produced in accordance with traditionalmanufacturing protocols with the exception that an amount of the CO₂sequestering composition is employed. In producing paper products of theinvention, an amount of the CO₂ sequestering composition may be employedas a filler, absorbent or colorant to the pulp composition. By“colorant” is meant a compound that is able to impart a color to aproduct. Since the CO₂ sequestering precipitate of the invention isinherently white in color, it is able to improve the white color ofalready white paper products, and lighten the color of paper productsthat are not white.

The pulp composition may be derived from components which include, butare not limited to eucalyptus pulp, banana tree bark, bananastem-fibers, cotton fibers, vulcanized polymers, cellulose fibers,animal skin (e.g., calfskin, sheepskin, goatskin), papyrus, high densitypolyethylene fibers, hemp, bamboo, grass, rags or pulp derived from thewood of any suitable tree. The moisture content of the pulp compositionmay vary, ranging from 5% to 10%, such as 6% and including 7%. In someinstances, the CO₂ sequestering composition may be added to the pulpcomposition as an absorbent in order to decrease the moisture content inthe paper.

The density of paper products of the invention may vary greatly. Thedensity of “paper” ranges from 100 kg/m³ to 1500 kg/m³, such as 250kg/m³ to 1250 kg/m³, including 500 kg/m³ to 800 kg/m³. The density of“papercard” or “card stock” ranges from 1500 kg/m³ to 3000 kg/m³, suchas 1700 kg/m³ to 2500 kg/m³, and including 2000 kg/m³ to 2250 kg/m³. Thedensity of “paperboard” can be 3000 kg/m³ and denser, such as 3500 kg/m³and denser, including 5000 kg/m³ and denser. The thickness of paperproducts the invention may also vary greatly. The thickness of “paper”ranges between 0.05 mm to 0.18 mm, such as 0.07 mm to 0.18 mm andincluding 0.1 mm to 0.15 mm. The thickness of “papercard” ranges between0.18 mm to 0.25 mm, such as 0.18 mm to 0.2 mm and including 0.19 mm. Thethickness of “paperboard” may be 0.25 mm and thicker, such as 0.3 mm andthicker, and including 1 mm and thicker. The weight of paper products ofthe invention may vary. By “weight” is meant the mass of paper productper unit area, usually measured in g/m². The weight of “paper” may rangebetween 20 g/m² to 160 g/m², such as 60 g/m² to 150 g/m² and including80 g/m² to 120 g/m². The weight of “papercard” may range between 160g/m² to 500 g/m², such as 175 g/m² to 400 g/m² and including 200 to g/m²to 300 g/m². The weight of “paperboard” may range from 500 g/m² andheavier, such as 750 g/m² and heavier and including 2000 g/m² andheavier.

In manufacturing paper products of the invention, the pulp compositionprecursors of the paper products may include one or more additionalcomponents, such as sizing agents, additional fillers (e.g., clay,china) and pigments. The amount of CO₂ sequestering additive in thefinished paper product may vary, and may be 1% by weight or more, suchas 3% by weight or more, including 5% by weight or more. Duringmanufacture, following production of the pulp with the CO₂ sequesteringadditive, the pulp may be pressed, dried and cut as desired to produce aproduct of desired dimensions. The paper may also be modified (e.g.,bleached, treated with a sizing agent or surface coating) after thefinished paper product has been produced.

Polymeric Products

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into polymeric products. The CO₂sequestering additive may be present in the polymeric product in variousamounts, as desired, and may be present as fillers and/or otherpurposes. As such, the amount of CO₂ sequestering additive in thepolymeric composition may vary, and may be 1% by weight or more, such as3% by weight or more, including 5% by weight or more. In certainembodiments, the polymeric products are plastics. The term “plastic” isused in its common sense to refer to a wide range of synthetic orsemisynthetic organic solid materials suitable for the manufacture ofindustrial products (e.g., films, fibers, plates, tubes, bottles,boxes). Plastics may be polymers of high molecular weight, and maycontain other substances to improve performance which may include butare not limited to acid scavengers, antimicrobial agents, antioxidants,antistatic agents, antifungal agents, clarifying agents, flameretardants, amine light stabilizers, UV absorbers, optical brighteners,photoselective additives, processing stabilizers, and the like. Plasticsof the invention may be acrylics, polyesters, silicones, polyurethanesor halogenated plastics. Plastics of interest include, but are notlimited to: polypropylenes (e.g., as employed in food containers,appliances, car bumpers), polystyrenes (e.g., as employed in packagingfoam, food containers, disposable cups, plates, cutlery, CD and cassetteboxes), high impact polystyrenes (e.g., as employed in fridge liners,food packaging, vending cups), acrylonitrile butadiene styrene (e.g., asemployed in electronic equipment cases such as computer monitors,printers, keyboards), polyethylene terephthalates (e.g., as employed incarbonated drinks bottles, jars, plastic film, microwavable packaging),polyesters (e.g., as employed in fibers, textiles), polyamides (e.g., asemployed in fibers, toothbrush bristles, fishing line, under-the-hoodcar engine mouldings), poly(vinyl chloride) (e.g., as employed inplumbing pipes and guttering, shower curtains, window frames, flooring),polyurethanes (e.g., as employed in cushioning foams, thermal insulationfoams, surface coatings, printing rollers) polycarbonates (e.g., asemployed in compact discs, eyeglasses, riot shields, security windows,traffic lights, lenses), polyvinylidene chloride (e.g., as employed infood packaging, saran), polyethylene (e.g., as employed in supermarketbags, plastic bottles) and polycarbonate/acrylonitrile butadiene styrene(e.g., as employed in car interior and exterior parts). Polymericproducts, such as plastics, of the invention may be prepared inaccordance with traditional manufacturing protocols for suchcompositions, with the exception that an amount of CO₂ sequesteringadditive of the invention is employed. As such, an amount of the CO₂sequestering additive may be combined with other additives of theplastic precursor composition or feed, and then molded, cast, extrudedinto the final desired plastic product.

Lubricants

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into lubricants. The CO₂ sequesteringcomposition may be present in the lubricants in various amounts, asdesired, and may be present as fillers and/or other purposes. The amountof CO₂ sequestering additive in the lubricant may vary, and may be 1% byweight or more, such as 3% by weight or more, including 5% by weight ormore. The lubricating oil composition may be formulated for commercialpurposes for use in internal combustion engines, such as gasoline anddiesel engines, crankcase lubrication and the like. The oil (sometimesreferred to as “base oil”) is an oil of lubricating viscosity and is theprimary liquid constituent of a lubricant, into which additives andpossibly other oils are blended to produce the final lubricant (herein“lubricating composition”). A base oil may be selected from natural(vegetable, animal or mineral) and synthetic lubricating oils andmixtures thereof. It may range in viscosity from light distillatemineral oils to heavy lubricating oils such as gas engine oil, minerallubricating oil, motor vehicle oil, and heavy duty diesel oil. In someinstances, the viscosity of the oil ranges from 2 to 30 mm²s⁻¹, such as5 to 20 mm²s⁻¹ at 100° C.

Natural oils include animal oils and vegetable oils, liquid petroleumoils and hydrorefined, solvent-treated or acid-treated minerallubricating oils of the paraffinic, naphthenic and mixedparaffinic-naphthenic types. Oils of lubricating viscosity derived fromcoal or shale are also useful base oils. Synthetic lubricating oilsinclude hydrocarbon oils and halo-substituted hydrocarbon oils such aspolymerized and interpolymerized olefins (e.g., polybutylenes,polypropylenes, propylene-isobutylene copolymers, chlorinatedpolybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes));alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes,dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g.,biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenylethers and alkylated diphenyl sulfides and the derivatives; analogs andhomologs thereof. Alkylene oxide polymers and interpolymers andderivatives thereof where the terminal hydroxyl groups have beenmodified, for example by esterification or etherification, constituteanother class of known synthetic lubricating oils. Another suitableclass of synthetic lubricating oils comprises the esters of dicarboxylicacids. Esters useful as synthetic oils also include those made from C₅to C₁₂ monocarboxylic acids and polyols, and polyol ethers such asneopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritoland tripentaerythritol. Silicon-based oils such as the polyalkyl-,polyaryl-, polyakoxy-, or polyaryloxysiloxane oils and silicate oilscomprise another useful class of synthetic lubricants.

Unrefined, refined and rerefined oils can be used in the lubricants ofthe present invention. Unrefined oils are those obtained directly from anatural or synthetic source without further purification treatment. Forexample, a shale oil obtained directly from retorting operations, apetroleum oil obtained directly from distillation or ester oil obtaineddirectly from an esterification process and used without furthertreatment would be an unrefined oil. Refined oils are similar to theunrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques, such as distillation, solvent extraction, acidor base extraction, filtration and percolation are known to thoseskilled in the art. Rerefined oils are obtained by processes similar tothose used to obtain refined oils applied to refined oils which havebeen already used in service. Such rerefined oils are also known asreclaimed or reprocessed oils and often are additionally processed bytechniques for removal of spent additives and oil breakdown products.Also present may be one or more co-additives. Known additives may beincorporated into the lubricant composition together with the additivesof the invention. They may, for example, include dispersants; otherdetergents, e.g. single or mixed detergent systems; rust inhibitors;anti-wear agents; anti-oxidants; corrosion inhibitors; frictionmodifiers or friction reducing agents; pour point depressants;anti-foaming agents; viscosity modifiers; and surfactants. They can becombined in proportions known in the art. Some additives can provide amultiplicity of effects; thus, for example, a single additive may act asa dispersant and as an oxidation inhibitor.

In certain instances, the additive is a dispersant. A dispersant is anadditive for a lubricant whose primary function is to hold solid andliquid contaminants in suspension, thereby passivating them and reducingengine deposits at the same time as reducing sludge depositions. Thus,for example, a dispersant maintains in suspension oil-insolublesubstances that result from oxidation during use of the lubricant, thuspreventing sludge flocculation and precipitation or deposition on metalparts of the engine. Dispersants are usually “ashless”, beingnon-metallic organic materials that form substantially no ash oncombustion, in contrast to metal-containing, and hence ash-forming,materials. They comprise a long chain hydrocarbon with a polar head, thepolarity being derived from inclusion of, e.g. an O, P or N atom. Thehydrocarbon is an oleophilic group that confers oil-solubility, havingfor example 40 to 500 carbon atoms. Thus, ashless dispersants maycomprise an oil-soluble polymeric hydrocarbon backbone having functionalgroups that are capable of associating with particles to be dispersed.Typically, the dispersants comprise amine, alcohol, amide, or esterpolar moieties attached to the polymer backbone often via a bridginggroup. The ashless dispersant may be, for example, selected fromoil-soluble salts, esters, amino-esters, amides, imides, and oxazolinesof long chain hydrocarbon-substituted mono- and dicarboxylic acids ortheir anhydrides; thiocarboxylate derivatives of long chainhydrocarbons; long chain aliphatic hydrocarbons having a polyamineattached directly thereto, and Mannich condensation products formed bycondensing a long chain substituted phenol with formaldehyde andpolyalkylene polyamine, such as described in U.S. Pat. No. 3,442,808.Dispersants include, for example, derivatives of long chainhydrocarbon-substituted carboxylic acids, examples being derivatives ofhigh molecular weight hydrocarbyl-substituted succinic acid.

A noteworthy group of dispersants are hydrocarbon-substitutedsuccinimides, made, for example, by reacting the above acids (orderivatives) with a nitrogen-containing compound, advantageously apolyalkylene polyamine, such as a polyethylene polyamine. Particularlypreferred are the reaction products of polyalkylene polyamines withalkenyl succinic anhydrides, such as described in U.S. Pat. Nos.3,202,678; 3,154,560; 3,172,892; 3,024,195, 3,024,237; 3,219,666; and3,216,936; and BE-A-66,875 that may be post-treated to improve theirproperties, such as borated (as described in U.S. Pat. Nos. 3,087,936and 3,254,025) fluorinated and oxylated. For example, boration may beaccomplished by treating an acyl nitrogen-containing dispersant with aboron compound selected from boron oxide, boron halides, boron acids andesters of boron acids. Also of interest are Anti-Wear and Anti-OxidantAgents. Dihydrocarbyl dithiophosphate metal salts are frequently used inlubricants as anti-wear and antioxidant agents. The metal may be analkali or alkaline earth metal, or aluminum, lead, tin, zinc,molybdenum, manganese, nickel or copper. The zinc salts are mostcommonly used in lubricating oil in amounts of 0.1 to 10, preferably 0.2to 2, mass %, based upon the total weight of the lubricant. They may beprepared in accordance with known techniques by first forming adihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of oneor more alcohols or a phenol with P₂S₅ and then neutralising the formedDDPA with a zinc compound. The zinc dihydrocarbyl dithiophosphates canbe made from mixed DDPA which in turn may be made from mixed alcohols.Alternatively, multiple zinc dihydrocarbyl dithiophosphates can be madeand subsequently mixed. Lubricants of the invention may be prepared inaccordance with traditional manufacturing protocols for suchcompositions, with the exception that an amount of CO₂ sequesteringadditive of the invention is employed. As such, an amount of the CO₂sequestering additive may be combined with other components of thelubricant and combined into the final desired lubricant product.

Adhesives

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into adhesives. By “adhesives” is meantcompounds that adhere to a substrate or bond two substrates together.Adhesives of the invention may be produced in accordance withtraditional manufacturing protocols with the exception that an amount ofthe CO₂ sequestering composition is employed. In producing adhesives ofthe invention, an amount of the CO₂ sequestering composition may beemployed as colorants, fillers, and to improve rheology and increasetensile strength.

The physical properties of adhesives of the invention may vary greatlydepending upon the type of chemical system employed and the amount ofthe CO₂ sequestering composition added. The viscosity may range from 1.0cP to 750000 cP, such as 100 cP to 10000 cP, including 500 cP to 5000cP, and including 1500 cP to 3000 cP. The effective temperature of theadhesive may range between −75° C. to 500° C., such as 0° C. to 200° C.and including 50° C. to 150° C. By “effective temperature” is meant thetemperature range in which the adhesive shows no significant changes inits physical properties or utility (i.e., insignificant change insubstrate bonding). The tensile strength of the adhesive may range from0.1 MPa to 75 MPa, such as 10 MPa to 50 MPa and including 15 to 35 MPa.The elongation capacity of the adhesives may range from 1.0% to 150%,such as 40% to 100% and including 50% to 75%.

When added, the CO₂ sequestering composition may increase the viscosity,the storage and loss moduli of the adhesive, and in some instances,impart pseudoplasticity and thixotropy. The amount of CO₂ sequesteringcomposition in adhesives of the invention may vary, ranging from 5 to40% by weight, such as 5 to 25% by weight and including 10 to 15% byweight.

Adhesives of the invention may be natural or synthetic. Naturaladhesives are made from inorganic mineral sources or biological sourcessuch as vegetable matter, dextrin or other natural resins. Syntheticadhesives usually comprise a chemical system (e.g., polymeric material),binders (e.g., polyester, polyurethane, acrylic resin), an aqueous ororganic solvent and one or more additives. Exemplary chemical systemsmay include polyoxymethylene, acrylic, polyacrylate, bismaleimide,butyl, cyanoacrylate, epoxy, ethylene copolymer, fluoropolymer,polyisoprene, polyamide, polyphenylene sulfide, polysulfide,polypropylene, polybutadiene, polyolefinic, polyester, polyurethane,polyphenolic, silicone, starch, polystyrene, styrene copolymer, vinyl,polyvinylcarbonate, rubber, elastomer, and compatible mixtures thereof.

In some embodiments, adhesives of the invention may be liquidcompositions which employ a solvent. Exemplary solvents may include, butare not limited to xylene, methanol, toluene, mineral spirits, acetone,butyl acetate, brominated solvents, mixtures thereof, among others. Theamount of solvent comprises about 10% to 90% of the liquid composition,such as 50% to 75%, including 60% to 70%. The liquid composition may beapplied by brushing, spraying, rolling, immersing the substrate into thecomposition, or any other convenient method for applying a coating to asurface. In some instances, depending on the amount of solvent, theliquid adhesive composition may be employed as a caulk or sealant.

In other instances, the liquid adhesive composition may be dispensedusing an aerosol sprayer by formulating the adhesive with a suitablepropellant. Exemplary propellants include, but are not limited tofluorinated propellants such as HFCs, hydrocarbons such as propane,butane, isobutane, pentane, nitrogen, carbon dioxide and any compatiblemixtures thereof. The amount of propellant may vary, ranging from 10% to30%, such as 15% to 25%, including 15% to 20%. The composition,including the sprayable propellant may be packaged into an aerosol byany convenient protocol.

In other embodiments, adhesives of the invention may be viscous liquids,gels, soft solids or powders. In producing the viscous liquid, softsolid, solid and gel adhesives, the components may be blended and mixedusing any convenient protocol. Exemplary methods for blending thecomponents include but are not limited to banbury mixers, sigman blademixers, double arm mixers, vortexing mixers, mixers that employsonication, mixers that employ heavy agitation, among others. Solid,soft solid and gel adhesives of the invention may then be further shapedby extruding, rotary pressing, stamping, cutting, laminating or moldingto produce the final adhesive product. In manufacturing adhesives of theinvention, the above mentioned constituents may also include one or moreadditional components, such as anti-foaming agents, wetting agents,thickeners, plasticizers, antioxidants and metal chelating agents.Tackifiers which increase the adhesion of the compositions in general orfor specific surfaces may also be added. Exemplary tackifiers includepolyterpene resins, gum rosin, rosin esters and other rosin derivatives,oil-soluble phenolic resins, coumaroneindene resins and petroleumhydrocarbon resins.

Methods of setting (i.e., curing) the adhesive product may include airdrying, anaerobic drying, thermoplastic setting, thermoset,two-component setting, UV or radiation cured, pressure induced setting,single component setting, moisture cured and vulcanization.

Adhesives of the invention may be compatible with use on a number ofdifferent types of substrates including but not limited to ceramic,glass, concrete, masonry, composite materials, metal, paper orpaperboard, plastic, porous surfaces, rubber, elastomer, textiles,fabrics or wood.

Rubber

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into rubber. The term “rubber” is usedin its conventional sense to mean an elastic material of varyingchemical composition which comprise long thread-like molecules andpossess a flexibility in its molecular chain to allow for overallmaterial flexing and coiling. Rubber of the invention may be produced inaccordance with traditional manufacturing protocols with the exceptionthat an amount of the CO₂ sequestering composition is employed. Inproducing rubber of the invention, an amount of the CO₂ sequesteringcomposition may be employed as colorants, fillers and to improveworkability of the raw rubber product. Rubber of the invention may benatural or synthetic. The term “natural” refers to rubber in the form ofa hydrocarbon polymer of isoprene units derived from the milky colloidalsuspension from the sap of a rubber tree or other such plants. Syntheticrubber may be derived from a number of different synthetic polymersincluding, but not limited to poly-styrene-butadiene, polyisobutylene,ethylene-propylene copolymer, polyneoprene, butadiene-acrylonitrilecopolymer, fluoroelastomers, polyurethane, polysulfide, polyacrylateamong others. Rubber of the invention may also include one or moreadditives, which include a vulcanizing agent, a vulcanizationaccelerator, a process oil, an anti-aging agent, an antioxidant and ananti-ozonant. In producing rubber of the invention, the components maybe blended or mixed with the CO₂ sequestering composition using anyconvenient protocol. Exemplary methods for blending the compositionsinclude banbury mixers, sigman blade mixers, double-arm mixers,vortexing mixers, mixers that employ sonication, mixers that employheavy agitation, among others. The rubber may be further shaped byrotary pressing, extruding, stamping, cutting, molding or any otherconvenient protocol into the final rubber product.

Chalk

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into chalk. The term “chalk” is used inits conventional sense to refer to a marking element usually in the formof a stick or block used for writing or drawing on a rough surface.Chalk in the present invention is a mixture of an amount of the CO₂sequestering composition with one or more thermosetting syntheticbinders which is further processed into the form of sticks or blocks.Binders used in the production of chalk may be any conventionalthermosetting synthetic binder. Exemplary binders include uncured epoxy,polyester, polyurethane or acrylic resins, or compatible mixturesthereof. Sticks or blocks of chalk are produced by forming a uniformmixture of the CO₂ sequestering composition with the synthetic binderand pressing it under high pressure at room temperature. The procedureis preferably such that the mixture of components are processed in anextrusion press, cooled and crushed to a fine particle size, such as 100microns or smaller, including 75 microns or smaller and preferably 60microns or smaller. The pulverulent mixture of components obtained isthen pressed at room temperature and under a pressure sufficient toconsolidate the powder (e.g., 10-35 MPa) into sticks or blocks of chalkyand friable consistency. Smaller sticks or blocks may also be cut fromlarger pre-pressed blocks. Colored chalk may also be produced using theabove described method, with the exception that a colorant (i.e., dye)may be added to the CO₂ sequestering composition and binder mixture.

Asphalt Products

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into asphalt products. The term“asphalt” (i.e., bitumen) is used in its conventional sense to refer tothe natural or manufactured black or dark-colored solid, semisolid orviscous material composed mainly of high molecular weight hydrocarbonsderived from a cut in petroleum distillation after naptha, gasoline,kerosene and other fractions have been removed from crude oil.

The molecular composition of asphalt products may vary. Asphalt productsof the invention may be composed of saturated and unsaturated aliphaticand aromatic compounds that possess functional groups that include, butare not limited to alcohol, carboxyl, phenolic, amino, thiol functionalgroups. In an exemplary embodiment, asphalt products may be 80% carbonby weight, 10% hydrogen by weight, 6% sulfur by weight, 3% total weightof oxygen and nitrogen; and may also include trace amounts of variousmetals such as iron, nickel and vanadium. The molecular weight ofasphalt products may range from 0.2 kDa to 50 kDa, such as 1 kDa to 25kDa, including 2 kDa to 10 kDa. Components of asphalts may beasphaltenes (i.e., high molecular weight compounds that are insoluble inhexane or heptane) or maltenes (i.e., lower molecular weight compoundsthat are soluble in hexane or heptane). The amount of asphaltenes inasphalt products may vary, ranging from 5% to 25% by weight, such as 10%to 20%, and including 12% to 15%. In some embodiments, asphalt productsof the invention may also contain a polymeric additive to enhanceworkability, viscoelasticity, and strain recovery. Exemplary polymericadditives include polybutadiene, polyisoprene, ethylene/vinyl acetatecopolymer, polyacrylate, polymethacrylate, polychloroprene, etc. Asphaltproducts of interest also include an amount of aggregate. Aggregate ofthe invention may be any convenient aggregate material. The aggregatematerial may be CO₂ sequestering aggregates, for example as described inU.S. patent application Ser. No. 12/475,378, titled “ROCK AND AGGREGATE,AND METHODS OF MAKING AND USING THE SAME”; the disclosure of which isherein incorporated by reference.

Asphalt products of the invention may be prepared in accordance withtraditional manufacturing protocols, with the exception that an amountof the CO₂ sequestering composition of the invention is employed. Theamount of CO₂ sequestering additive, e.g., present in the asphaltproduct may vary, and may be 1% by weight or more, such as 3% by weightor more, including 5% by weight or more, such as 25% by weight or more,50% by weight or more, 75% by weight or more. As such, an amount of theCO₂ sequestering additive may be combined with other components of theasphalt product (e.g., asphalt, aggregate, cutback solvents, polymericadditives), and then mixed to produce the final asphalt product.

Paint

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into paint. By “paint” is meant anyliquid, liquefiable, or mastic composition which, after application to asubstrate in a thin layer, is converted to an opaque solid film. Paintsmay include one or more of the following components: pigments, binders,solvents and additives. Pigments are granular solids incorporated intothe paint, e.g., to contribute color, toughness or simply to reduce thecost of the paint. Pigments of interest include natural and synthetictypes. Natural pigments include various clays, calcium carbonate, mica,silicas, and talcs. Synthetic pigments include engineered molecules,calcined clays, blanc fix, precipitated calcium carbonate, and syntheticsilicas. Hiding pigments, in making paint opaque, also protect thesubstrate from the harmful effects of ultraviolet light. Hiding pigmentsinclude titanium dioxide, phthalo blue, red iron oxide, and many others.Fillers are a special type of pigment that serve to thicken the film,support its structure and simply increase the volume of the paint.Fillers of interest include inert materials, such as talc, lime, baryte,clay, etc. Floor paints that will be subjected to abrasion may evencontain fine quartz sand as a filler. Not all paints include fillers. Onthe other hand some paints contain very large proportions ofpigment/filler and binder. The CO₂ sequestering additive of theinvention may be employed in place of all or some of the above pigmentcomponents in a given paint. The binder, or resin, is the actual filmforming component of paint. The binder imparts adhesion, binds thepigments together, and strongly influences such properties as glosspotential, exterior durability, flexibility, and toughness. Binders ofinterest include synthetic or natural resins such as acrylics,polyurethanes, polyesters, melamine resins, epoxy, or oils, etc.Solvents of interest may be present, e.g., to adjust the viscosity ofthe paint. They may be volatile so as not to become part of the paintfilm. Solvents may be included to control flow and applicationproperties, and affect the stability of the paint while in liquid state.Solvents of interest include water, e.g., water-based paints and organicsolvents, e.g., aliphatics, aromatics, alcohols, and ketones. Organicsolvents such as petroleum distillate, esters, glycol ethers, and thelike find use. Additives of interest include additives to modify surfacetension, improve flow properties, improve the finished appearance,increase wet edge, improve pigment stability, impart antifreezeproperties, control foaming, control skinning, etc. Other types ofadditives include catalysts, thickeners, stabilizers, emulsifiers,texturizers, adhesion promoters, UV stabilizers, flatteners (de-glossingagents), biocides to fight bacterial growth, and the like.

Paint products of the invention may be prepared in accordance withtraditional manufacturing protocols with the exception that an amount ofCO₂ sequestering additive of the invention is employed. The amount ofCO₂ sequestering additive in the paint may vary, and may be 1% by weightor more, such as 3% by weight or more, including 5% by weight or more,such as 25% by weight or more. As such, an amount of the CO₂sequestering additive may be combined with other components of the paintsuch as pigment, binder, solvent, additive and then mixed to produce thefinal paint product.

Personal Care, Cleaning and Other Non-Ingestible Products

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into non-ingestible products. By“non-ingestible” is meant compounds that are not suitable forconsumption. Of interest are novel non-ingestible formulations whichincorporate the CO₂ sequestering composition of the invention intopersonal care products. Personal care products of the invention arecompositions intended for cleaning purposes or personal use such as forhealth and/or hygiene purposes. Personal care products may be productsthat relate to sun-care (e.g., sunscreens, sun-tan lotion, self tanningcompositions, bronzers), baby-care (e.g., diapers, baby wipes, babypowder, diaper rash products), facial and body treatment (e.g., acneprevention wipes, acne treatment cream, facial cleansing soap andexfoliating soap, antiperspirants, deodorants, aftershave lotion, bathsoap, bath wash, shaving cream, shaving gel, makeup removal,moisturizers, anti-wrinkle creams, lotions), foot-care (anti-itch cream,anti-fungal creams), oral-care (toothpaste, mouthwash), hair-care(shampoo, conditioner, hair spray, hair gel, mouse, colorants,depilatory treatments, hair bleach) and First Aid (bandages, antisepticsprays, antibacterial gels). Another type of personal care product iscosmetics. Cosmetics of the invention are makeup products that include,but are not limited to mascara, eyeshadow, eyeliner, blush, concealer,foundation, face powder, lipstick, lip gloss, lip treatment, liplinerand nail polish. Another type of personal care product are cleaningproducts. Cleaning products of the invention are compounds usedprimarily in the removal of dirt, stains, impurities, microorganisms andthe like. Cleaning products of the invention may be products that relateto laundry cleaners (e.g., laundry detergent, stain remover, fabricsoftener), dishwashing products (dishwashing liquid, dishwashingpowders, dishwashing gels, rinse agents, fast-dry agents), roomdeodorizing products, bathroom cleaners (toilet, shower, marble,porcelain), powdered bleach, shoe polish and all-purpose cleaners.

The CO₂ sequestering composition of the invention may be employed innon-ingestible products as an abrasive, absorbent, buffering agent,filler, anti-caking agent, colorant, opacifying agent, UV-scatteringagent or oral care agent. Traditional abrasives, absorbents, bufferingagents, fillers, colorants, anti-caking agents, opacifying agents,UV-scattering agents or oral care agents that are conventionally foundin non-ingestible products may be substituted entirely or a certainamount removed and replaced using the CO₂ sequestering composition ofthe present invention. The CO₂ sequestering composition used to replacetraditional additives may be present in amounts such as 1% by weight ormore, such as 3% by weight or more, including 5% by weight or more, suchas 25% by weight or more, 50% by weight or more, 75% by weight or more.

In some embodiments, the CO₂ sequestering composition of the inventionmay be employed in non-ingestible products as an abrasive. By “abrasive”is meant a compound that contains an amount of roughness which when usedon a surface is able to abrade, smooth, buff, polish, grind and thelike. The roughness of the abrasive may vary, depending on the particlesizes of the CO₂ sequestering composition. In some instances, theparticle sizes of the CO₂ sequestering composition are small (≦0.5micron) and may be incorporated into non-ingestible products where onlya mild abrasive is desired (e.g., bathroom cleaners, baby wipes). Inother instances, the particle sizes of the CO₂ sequestering precipitateare large (≧5 micron) and may be incorporated into non-ingestibleproducts where a strong abrasive is desired (e.g., bath soap,toothpaste). Exemplary non-ingestible products of the inventionemploying the CO₂ sequestering composition as an abrasive includetoothpaste, shoe polish, mouthwash, facial cleansing soaps, exfoliatingproducts, acne prevention wipes, bath soap, bath wash, makeup remover,baby wipes, diaper rash products, bathroom cleaners, powdered bleach andall purpose cleaners. In some embodiments, the CO₂ sequesteringcomposition is employed as an abrasive for paint removal, such as inprocesses employing blasting techniques wherein the abrasive issuspended in a liquid and applied to a painted or coated surface. TheCO₂ sequestering composition may be used as an abrasive for paintremoval in cases where the surfaces are delicate, such as lightweightmetal and plastic surfaces, in some embodiments of the invention.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in non-ingestible products as an absorbent. By“absorbent” is meant a compound that possesses the capacity to absorb orsoak up liquids (i.e., drying agent). Exemplary non-ingestible productsof the invention employing the CO₂ sequestering composition as anabsorbent include eyeshadow, blush, concealer, foundation, face powder,sunscreen, sun-tan lotion, self tanning compositions, bronzers, babypowder, diaper rash products, deodorants and antiperspirants.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in non-ingestible products as an anticaking agent. By“anticaking agent” is meant a compound that prevents solid compositionsfrom forming large aggregates (i.e., clumps) and facilitates aconsistent granular or powdered composition. Exemplary non-ingestibleproducts of the invention employing the CO₂ sequestering composition asan anticaking agent include baby powder, foundation, face powder, blush,eyeshadow, diaper rash products, concealer, laundry detergent,dishwashing powder, rinse agents, fast-dry agents, room deodorizingpowders, bathroom cleaners and powdered bleach.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in non-ingestible products as a buffering agent. By“buffering agent” is meant a compound that minimizes changes in pH. Assuch, the CO₂ sequestering component may act to buffer any acidic orbasic components traditionally used in formulations for these productsor may be used to maintain a suitable pH during its use. Exemplarynon-ingestible products of the invention employing the CO₂ sequesteringcomposition as a buffering agent include lip gloss, nail polish,sunscreens, sun-tan lotion, baby wipes, acne prevention wipes, acnetreatment cream, facial cleansing soap and exfoliating soap,antiperspirants, deodorants, aftershave lotion, bath soap, bath wash,shaving cream, shaving gel, makeup removal, moisturizers, anti-wrinklecreams, anti-drying lotions, anti-itch cream, anti-fungal creams,conditioner, hair spray, hair gel, mouse, hair colorants, depilatorytreatments, hair bleach, antiseptic sprays, antibacterial gels, laundrydetergent, stain remover, teeth whitening agents, dishwashing liquid,dishwashing powders, dishwashing gels, rinse agents, fast-dry agents,bathroom cleaners and all-purpose cleaners.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in non-ingestible products as a filler. By “filler” ismeant a non-reactive, solid ingredient used to dilute other solids, orto increase the volume of a product. In some instances, the CO₂sequestering composition may be used to dilute a potent activeingredient, which may be present in very small amounts, so that theproduct can be handled more easily. In other instances, the CO₂sequestering composition may be used to increase the volume of anexpensive ingredient without disturbing the main function of theproduct. Exemplary non-ingestible products of the invention employingthe CO₂ sequestering composition as a filler include baby powder,foundation, face powder, blush, eyeshadow, diaper rash products,concealer, laundry detergent, dishwashing powder, rinse agents, fast-dryagents, room deodorizing powders, bathroom cleaners and powdered bleach.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in non-ingestible products as a colorant. By “colorant”is meant a compound that is able to impart a color to a product. Sincethe CO₂ sequestering precipitate of the invention is inherently white incolor, it is able to improve the white color of already white products,and lighten the color of those products that are not white. Exemplarynon-ingestible products of the invention employing the CO₂ sequesteringcomposition as a filler include eyeshadow, blush, concealer, foundation,face powder, sunscreens, sun-tan lotion, self tanning compositions,bronzers, baby powder, acne treatment cream, facial cleansing soap,exfoliating soap, antiperspirants, deodorants, bath soap, bath wash,shaving cream, moisturizers, anti-wrinkle cream, teeth whitening agents,lotions, anti-inch cream, anti-fungal cream, toothpaste, shampoo,conditioner, hair mousse, hair colorants, laundry detergent, dishwashingpowders and room deodorizing products.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in non-ingestible products as an opacifying agent. By“opacifying agent” is meant a substance that reduces the clear ortransparent appearance of a product. The opacity of the non-ingestibleproduct may vary depending on the particle sizes of the CO₂ sequesteringcomposition. For substantially opaque materials (e.g., anti-wrinklecream), large particle sizes may be used (≧1 micron). For compositionswhere a less substantial opacity is desired, small particles may be used(≦0.5 micron). Exemplary non-ingestible products of the inventionemploying the CO₂ sequestering composition as an opacifying agentinclude anti-wrinkle cream, bronzer, sun-tan lotion and self-tanningcompositions.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in non-ingestible products as an oral-care agent. By“oral-care agent” is meant a compound that may be used to polish teeth,reduce oral odor or otherwise cleanse or deodorize the teeth and mouth.In addition to being a mild abrasive for polishing teeth, the CO₂sequestering composition, when incorporated in products used for oralhygiene, can buffer acids that facilitate tooth decay and provide awhitening component to oral-care products. Exemplary non-ingestibleproducts of the invention employing the CO₂ sequestering composition asan oral-care agent include toothpaste, teeth whitening agents andmouthwash.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in non-ingestible products as a UV-scattering agent. By“UV-scattering agent” is meant a compound that can sufficiently scatterUV light. Depending on the particle sizes of the CO₂ sequesteringprecipitate, the amount of UV light (i.e., light having wavelengths≦380nm) that is scattered and thus unavailable for absorption may vary. Insome instances, the amount of UV light scattered may be 10% or more,including 25% or more, such as 50% or more. In some embodiments of theinvention, the CO₂ sequestering composition may be the only componentused to protect against UV radiation. In other embodiments, the CO₂sequestering composition may be used in combination with conventional UVabsorbing compositions to protect against UV radiation. Exemplarynon-ingestible products of the invention employing the CO₂ sequesteringcomposition as a UV-scattering agent include sunscreen, face powder,blush and foundation.

Food, Vitamins, Nutritional Supplements, Pharmaceuticals and OtherIngestible Products

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into ingestible products. By“ingestible” is meant compositions that are taken orally, even thoughthey may not be digested, where ingestibles are formulated for humanconsumption. Ingestibles of the invention may include food products,vitamins, nutritional supplements, pharmaceuticals and mineral fortifiedproducts.

Of interest are novel ingestible formulations which incorporate the CO₂sequestering composition of the invention into food products. Foodproducts of the invention are any ingestible solids or liquids, usuallycomposed of carbohydrates, fats, water and/or proteins that are consumedfor nutrition or pleasure. In certain embodiments, the CO₂ sequesteringcomposition of the invention may be employed in food products as abuffering agent, filler, anti-caking agent, colorant, emulsifier orstabilizer. Traditional buffering agents, fillers, anti-caking agents,colorants, emulsifiers and stabilizers conventionally found in foodproducts may be substituted entirely or a certain amount removed andreplaced by the CO₂ sequestering compositions of the present invention.

In some embodiments, the CO₂ sequestering composition of the inventionmay be employed in food products as a buffering agent. As describedabove, the CO₂ sequestering composition may act to minimize pH changescaused by any acidic or basic components traditionally used informulations for these products or may be used to maintain a suitable pHfor taste. Exemplary food products of the invention employing the CO₂sequestering composition as a buffering agent include condiments, fatemulsions (e.g., salad dressings) water-based flavored drinks (e.g.,energy drinks, sports drinks, electrolyte drinks), soybean products(e.g., soy sauce), processed fruits, canned fruits, processedvegetables, canned vegetables, processed meats, canned meats, beer,wine, cider, malt beverages and canned soups.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in food products as a filler. As described above, afiller is a non-reactive, solid ingredient used to dilute other solids,or to increase the volume of a product. Exemplary food products of theinvention employing the CO₂ sequestering composition as a filler includeseasonings, dairy-based products, confectionary substances, baby food,baby formula, sweeteners, milk powders, edible casings and milksubstitutes.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in food products as an anti-caking agent. As describedabove, an anti-caking agent is used to prevent solid compositions fromforming large aggregates (i.e., clumps) and facilitates a consistentgranular or powdered composition. Exemplary food products of theinvention employing the CO₂ sequestering composition as an anti-cakingagent include milk powders, baby formula, confectionary substances,sweeteners and seasonings.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in food products as an emulsifier. By “emulsifier” ismeant a substance that forms or maintains a uniform mixture of two ormore immiscible phases. In some instances, the CO₂ sequesteringcomposition can be used to form a mixture of oil and water in foodproducts. Exemplary food products of the invention employing the CO₂sequestering composition as an emulsifier include fat emulsions (e.g.,salad dressings), broths and condiments.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in food products as a colorant. As described above, acolorant is a compound that is able to impart a color to a product.Since the CO₂ sequestering precipitate of the invention is inherentlywhite in color, it is able to improve the white color of already whiteproducts, and lighten the color of those products that are not white.Exemplary food products of the invention employing the CO₂ sequesteringcomposition as a colorant include dairy based products, milksubstitutes, milk powder, sweeteners, seasonings, baby formula, driedegg products and confectionary substances.

In other embodiments, the CO₂ sequestering composition of the inventionmay be employed in food products as a stabilizer. By “stabilizer” ismeant a substance that facilitates a uniform dispersion of two or moreimmiscible substances. Exemplary food products of the inventionemploying the CO₂ sequestering composition as a stabilizer include dairybased products, canned soups, milk substitutes, liquid whey andcondiments.

Also of interest are novel ingestible formulations which incorporate theCO₂ sequestering composition of the invention into vitamins, nutritionalsupplements and pharmaceuticals. Vitamins, nutritional supplements andpharmaceuticals of the invention may include any ingestible solids orliquids that are not food products (as described above) consumed fornutritional or medicinal purposes. In certain embodiments, the CO₂sequestering composition of the invention may be employed in vitamins,nutritional supplements and pharmaceuticals as buffering agents,fillers, anti-caking agents, colorants, and binders. By “binder” ismeant a substance that is used to hold together ingredients of acompressed tablet or cake. Vitamins, nutritional supplements andpharmaceuticals of the invention may be in the form or a powder, syrup,liquid, tablet, capsule with powder filling, liquid-gel capsule and thelike. Vitamins, nutritional supplements and pharmaceuticals may include,but are not limited to over-the-counter medications, behind-the-countermedications, prescription medications, liquid nutritional drinks,nutritional powders, weight-loss supplements, multivitamins,nutraceuticals, laxatives, antacids and the like. Traditional bufferingagents, fillers, anti-caking agents, colorants and bindersconventionally found in vitamins, nutritional supplements andpharmaceuticals may be substituted entirely or a certain amount removedand replaced by the CO₂ sequestering compositions of the presentinvention.

An exemplary embodiment, depending upon the components in the water andthe gaseous stream used to generate the carbonate precipitate of theinvention (as described in detail below) include preparing the CO₂sequestering carbonate precipitate in tablet form for use as a dietarysupplement or as an antacid (e.g., calcium supplement). Substantiallypure calcium and magnesium carbonate precipitate provided by methods ofthe invention may be further processed into tablets by any convenientprotocol. The CO₂ sequestering carbonate precipitate may also beincorporated into tablets containing multiple dietary supplements (e.g.,multivitamin).

In another exemplary embodiment, the CO₂ sequestering composition ofinvention may be used for the mineral fortification of food products. By“mineral fortification” is meant the addition of minerals (e.g.,calcium, magnesium) to food during production or processing. Foodproducts of the invention may be fortified with minerals bysubstantially pure CO₂ sequestering carbonate precipitate using anyconvenient protocol, such as for example mixing the CO₂ sequesteringcomposition with the food product.

Depending on the type of food product, the amount of CO₂ sequesteringcomposition added may vary, ranging from 5 mg to 1500 mg, such as 10 mgto 500 mg and including 100 mg to 200 mg. Exemplary food products thatmay be fortified with CO₂ sequestering compositions of the inventioninclude, but are not limited to: baked goods (e.g., breads, cookies,biscuits, crackers, waffles, pancakes, cakes); bars (e.g., baked bars,breakfast bars, granola bars, energy bars); beverages (e.g., opaquebeverages, both dairy and non-dairy); breakfast cereals; chewing gum;candies (e.g., opaque hard candies, chocolate, nougats, caramels, creamfilled); frozen desserts (e.g., ice cream, frozen soy desserts, frozenyogurts); infant formulas; ingredient enrichment (e.g., flour, meals,grains, wheat, corn, rice, oats); liquid meals (e.g., replacement meals,special formulations for diabetic, diet or slimming drinks); milks;pastas (e.g., macaroni, spaghetti, noodles, couscous, ramen, instantnoodles); powdered drink mixes (e.g., flavored milks, energy drinks,protein drinks); probiotics; soymilks; tofu; yogurts (e.g.,bulk-fermented yogurts, drinkable yogurts, yogurt-based smoothies).

Animal Ingestible Products

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into animal ingestible products. By“animal ingestible” is meant compositions that are taken orally and areformulated for non-human (e.g., livestock, pets) consumption AnimalIngestible products of the invention may include but are not limited toanimal food products, vitamins, nutritional supplements andpharmaceuticals for animal consumption. Of interest are novelanimal-ingestible product formulations which employ the CO₂ sequesteringcomposition of the invention as buffering agents, fillers, anti-cakingagents, colorants, emulsifiers, stabilizers and binders into foodproducts, vitamins, nutritional supplements and pharmaceuticalsformulated for animal consumption. Traditional buffering agents,fillers, anti-caking agents, colorants, emulsifiers, stabilizers andbinders conventionally found in animal-ingestible products may besubstituted entirely or a certain amount removed and replaced by the CO₂sequestering compositions of the present invention.

Agricultural Products

The present invention also includes novel formulations which incorporatethe CO₂ sequestering composition into agricultural products. By“agricultural products” is meant any composition that is employed incultivating land, raising crops or vegetation, farming, and feeding,breeding, and raising livestock or any other activity associatedtherewith. Agricultural products of the invention may be soil amendmentcompositions (e.g., fertilizer, remediation), pest control (fungicides,insecticides) or nutritional and/or medicinal ingestible compositionsfor livestock (as detailed above). The CO₂ sequestering composition ofthe invention may be added to traditional agricultural products as asupplement or entirely replace conventionally used agriculturalproducts.

In some embodiments, the CO₂ sequestering composition of the inventionis a soil amendment. By “soil amendment” is meant a composition thataims to improve or remediate the desired properties of soil foragricultural usage. In some instances the soil amendment is a fertilizerto supply nutrients (e.g., calcium, magnesium) to the soil. In otherinstances, the soil amendment is a buffering agent to reduce changes tothe pH of the soil. The CO₂ sequestering composition of the inventionmay be contacted with the soil in the form of a slurry or a powder. TheCO₂ sequestering precipitate is either mixed with water prior to beingdispensed onto the surface of the soil or is dispensed as a dry powder.Contacting the composition with the soil may be achieved using anyconvenient protocol. It may be gravity fed or pumped through hoses,spray nozzles or fixed sprayers to uniformly apply the composition. Inother instances, the CO₂ soil stabilization compositions of theinvention may be poured from a reservoir or applied manually without theuse of any industrial machinery. The composition may also be applied byreleasing the composition at a depth within the soil by pumping thecomposition beneath the surface of the soil to be treated or by diggingto a depth in the soil using conventional digging machinery and furtherapplying the composition. The composition is then mixed into the soil.In any of the various treatments within the scope of the presentinvention, the soil may be mixed in situ or may be temporarily removedfrom the ground for mixing and then replaced. Mixing the soil with theCO₂ sequestering composition may be accomplished using any convenientmixing equipment (e.g., rotary mixers, cement mixers, etc.). Theprepared CO₂-sequestering composition and soil mixture is then rotatedand the entire mixture is blended in a uniform manner.

In other embodiments, the CO₂ sequestering composition of the inventionmay be incorporated into pesticides. The term “pesticide” is used in itsconventional sense to mean any compound that is used to eliminate,control or inhibit the proliferation of any organism which hascharacteristics that are regarded as injurious or unwanted. Pesticidesof the invention may include those formulations used against insects,fungi, bacteria, rodents and the like. The CO₂ sequestering compositionmay be employed in pesticides to improve the pesticide action or to aidin the application of the pesticide. For example, the CO₂ sequesteringcomposition may be employed as a water absorbent or as a granulatingagent. In other instances, the composition may be employed as acrop-dusting filler to facilitate the uniform distribution of thepesticide on vegetation or crops. Pesticides of the invention may beprepared using any conventional protocol with the exception that anamount of the CO₂ sequestering composition is added. The amount of CO₂sequestering additive in the pesticide may vary, and may be 1% by weightor more, such as 3% by weight or more, including 5% by weight or more,such as 25% by weight or more. The CO₂ sequestrating composition may beincorporated into the pesticides during the formulation of the pesticideor may be subsequently added to the finished pesticide product.Incorporation of the composition into the pesticide may be accomplishedby mixing the composition with the pesticide and rotating the mixtureunder agitation, vortex or sonication and blending into a uniformpesticide product.

Environmental Remediation

The CO₂ sequestering composition of the invention may also be employedin environmental remediation. By “environmental remediation” is meantthe removal of pollution or contaminants from environmental media suchas soil, groundwater, sediment or water for the general protection ofhuman health and the environment.

In some embodiments, environmental remediation employing the CO₂sequestering composition of the invention is forest soil restoration.The application of the CO₂ sequestering composition may be employed inforest soil restoration for neutralizing acidic soil, improving thecalcium and magnesium content in soil, increasing the biologicalactivity of organically influenced soil horizons, intensifying thenitrification process in the soil or stabilizing metal organic complexesin order to decrease or prevent heavy-metal pollution. The CO₂sequestering composition of the invention may be contacted with theforest soil using any convenient protocol (as discussed above). It maybe applied using devices that are gravity fed or it can be pumpedthrough hoses, spray nozzles or fixed sprayers. The composition may alsobe poured from a reservoir or applied manually without the use of anyindustrial machinery. In some instances, the CO₂ sequesteringcomposition may be dispensed from a helicopter or crop-dusting airplane.

In other embodiments, environmental remediation employing the CO₂sequestering composition of the invention is the neutralization ofover-acidified water. By “acidified water” is meant a large body ofwater (e.g., pond, lake) that has a pH below 6.5 under ambientconditions and is often lower, such as 6.0 and including 5.0. The CO₂sequestering composition can be applied by any convenient protocol. Insome instances, the composition is applied as a slurry or as a finelyground powder. Slurries are typically sprayed onto the water surfacefrom boats or from stations located on the water, whereas powder isdispensed by helicopter or fixed-wing planes. The application of the CO₂sequestering composition may cause increases in pH that vary rangingfrom 1 to 4, including 2 to 4, such as 2.5 to 3.5. The amount of the CO₂sequestering composition applied to the acidified water may varyconsiderably (depending on the size and location of the body of waterand the pH of the water) ranging from 0.1 kg to 100 kg or more, such as1000 kg or more, including 10,000 kg or more.

Preparation of CO₂ Sequestering Compositions

Aspects of the invention also include methods of preparing CO₂sequestering compositions. CO₂ sequestering compositions may be preparedby producing a CO₂ sequestering additive, e.g., as described above, andthen preparing the composition from the component. Each of these aspectsof the invention will now be described in greater detail.

A variety of different methods may be employed to prepare the CO₂sequestering additive of the compositions of the invention. CO₂sequestration protocols of interest include, but are not limited to,those disclosed in U.S. patent application Ser. Nos. 12/126,776, titled,“Hydraulic cements comprising carbonate compound compositions,” filed 23May 2008; 12/163,205, titled “DESALINATION METHODS AND SYSTEMS THATINCLUDE CARBONATE COMPOUND PRECIPITATION,” filed 27 Jun. 2008; and12/486,692, titled “METHODS AND SYSTEMS FOR UTILIZING WASTE SOURCES OFMETAL OXIDES” filed 17 Jun. 2009; 12/501,217, titled “PRODUCTION OFCARBONATE-CONTAINING COMPOSITIONS FROM MATERIAL COMPRISING METALSILICATE,” filed 10 Jul. 2009; and 12/557,492, titled “CO2 COMMODITYTRADING SYSTEM AND METHOD,” filed 10 Sep. 2009; as well as InternationalApplication No. PCT/US08/88318, titled, “METHODS OF SEQUESTERING CO₂,”filed 24 Dec. 2008; and PCT/US09/45722, titled “ROCK AND AGGREGATE, ANDMETHODS OF MAKING AND USING THE SAME,” filed 29 May 2009; as well aspending U.S. Provisional Patent Application Ser. Nos. 61/081,299;61/082,766; 61/088,347; 61/088,340; and 61/101,631; the disclosures ofwhich are herein incorporated by reference.

CO₂ sequestering additives of the invention include carbonatecompositions that may be produced by precipitating a calcium and/ormagnesium carbonate composition from a water. The carbonate compoundcompositions that make up the CO₂ sequestering additives of theinvention include may metastable carbonate compounds that may beprecipitated from a water, such as a salt-water, as described in greaterdetail below. The carbonate compound compositions of the inventioninclude precipitated crystalline and/or amorphous carbonate compounds.

In certain embodiments, the water from which the carbonate precipitatesare produced is a saltwater. In such embodiments, the carbonate compoundcomposition may be viewed as a saltwater derived carbonate compoundcomposition. As used herein, “saltwater-derived carbonate compoundcomposition” means a composition derived from saltwater and made up ofone or more different carbonate crystalline and/or amorphous compoundswith or without one or more hydroxide crystalline or amorphouscompounds. The term “saltwater” is employed in its conventional sense torefer to a number of different types of aqueous liquids other than freshwater, where the term “saltwater” includes brackish water, sea water andbrine (including man-made brines, e.g., geothermal plant wastewaters,desalination waste waters, etc), as well as other salines having asalinity that is greater than that of freshwater. Brine is watersaturated or nearly saturated with salt and has a salinity that is 50ppt (parts per thousand) or greater. Brackish water is water that issaltier than fresh water, but not as salty as seawater, having asalinity ranging from 0.5 to 35 ppt. Seawater is water from a sea orocean and has a salinity ranging from 35 to 50 ppt. The saltwater sourcefrom which the mineral composition of the cements of the invention isderived may be a naturally occurring source, such as a sea, ocean, lake,swamp, estuary, lagoon, etc., or a man-made source. In certainembodiments, the saltwater source of the mineral composition isseawater.

While the present invention is described primarily in terms of saltwatersources, in certain embodiments, the water employed in the invention maybe a mineral rich, e.g., calcium and/or magnesium rich, freshwatersource. The water employed in the process is one that includes one ormore alkaline earth metals, e.g., magnesium, calcium, etc, and isanother type of alkaline-earth-metal-containing water that finds use inembodiments of the invention. Waters of interest include those thatinclude calcium in amounts ranging from 50 to 20,000 ppm, such as 100 to10,0000 ppm and including 200 to 5000 ppm. Waters of interest includethose that include magnesium in amounts ranging from 50 to 20,000 ppm,such as 200 to 10000 ppm and including 500 to 5000 ppm.

The saltwater-derived carbonate compound compositions of embodiments ofthe cements are ones that are derived from a saltwater. As such, theyare compositions that are obtained from a saltwater in some manner,e.g., by treating a volume of a saltwater in a manner sufficient toproduce the desired carbonate compound composition from the initialvolume of saltwater. The carbonate compound compositions of certainembodiments are produced by precipitation from a water, e.g., asaltwater, a water that includes alkaline earth metals, such as calciumand magnesium, etc., where such waters are collectively referred to asalkaline-earth-metal-containing waters.

The saltwater employed in methods may vary. As reviewed above,saltwaters of interest include brackish water, sea water and brine, aswell as other salines having a salinity that is greater than that offreshwater (which has a salinity of less than 5 ppt dissolved salts. Insome embodiments, calcium rich waters may be combined with magnesiumsilicate minerals, such as olivine or serpentine, in solution that hasbecome acidic due to the addition on carbon dioxide to form carbonicacid, which dissolves the magnesium silicate, leading to the formationof calcium magnesium silicate carbonate compounds as mentioned above.

In methods of producing the carbonate compound compositions of theaggregates of the invention, a volume of water is subjected to carbonatecompound precipitation conditions sufficient to produce a precipitatedcarbonate compound composition and a mother liquor (i.e., the part ofthe water that is left over after precipitation of the carbonatecompound(s) from the saltwater). The resultant precipitates and motherliquor collectively make up the carbonate compound compositions of theinvention. Any convenient precipitation conditions may be employed,which conditions result in the production of a carbonate compoundcomposition sequestration product.

Precipitation conditions of interest may vary. For example, thetemperature of the water may be within a suitable range for theprecipitation of the desired mineral to occur. In some embodiments, thetemperature of the water may be in a range from 5 to 70° C., such asfrom 20 to 50° C. and including from 25 to 45° C. As such, while a givenset of precipitation conditions may have a temperature ranging from 0 to100° C., the temperature of the water may have to be adjusted in certainembodiments to produce the desired precipitate.

In normal sea water, 93% of the dissolved CO₂ is in the form ofbicarbonate ions (HCO₃ ⁻) and 6% is in the form of carbonate ions (CO₃⁻²). When calcium carbonate precipitates from normal sea water, CO₂ isreleased. In fresh water, above pH 10.33, greater than 90% of thecarbonate is in the form of carbonate ion, and no CO₂ is released duringthe precipitation of calcium carbonate. In sea water this transitionoccurs at a slightly lower pH, closer to a pH of 9.7. While the pH ofthe water employed in methods may range from 5 to 14 during a givenprecipitation process, in certain embodiments the pH is raised toalkaline levels in order to drive the precipitation of carbonatecompounds, as well as other compounds, e.g., hydroxide compounds, asdesired. In certain of these embodiments, the pH is raised to a levelwhich minimizes if not eliminates CO₂ production during precipitation,causing dissolved CO₂, e.g., in the form of carbonate and bicarbonate,to be trapped in the carbonate compound precipitate. In theseembodiments, the pH may be raised to 10 or higher, such as 11 or higher.

The pH of the water may be raised using any convenient approach. Incertain embodiments, a pH raising agent may be employed, where examplesof such agents include oxides, hydroxides (e.g., calcium oxide in flyash, potassium hydroxide, sodium hydroxide, brucite (Mg(OH₂), etc.),carbonates (e.g., sodium carbonate) and the like. One such approach isto use the coal ash from a coal-fired power plant, which contains manyoxides, to elevate the pH of the water. Other coal processes, like thegasification of coal, to produce syngas, also produce hydrogen gas andcarbon monoxide, and may serve as a source of hydroxide as well. Somenaturally occurring minerals, such as serpentine, contain hydroxide, andcan be dissolved, yielding a hydroxide source. The addition ofserpentine, also releases silica and magnesium into the solution,leading to the formation of silica containing carbonate compounds. Theamount of pH elevating agent that is added to the water will depend onthe particular nature of the agent and the volume of water beingmodified, and will be sufficient to raise the pH of the water to thedesired value. Alternatively, the pH of the water source can be raisedto the desired level by electrolysis of water. Where electrolysis isemployed, a variety of different protocols may be taken, such as use ofthe Mercury cell process (also called the Castner-Kellner process); theDiaphragm cell process and the membrane cell process. Where desired,byproducts of the hydrolysis product, e.g., H₂, sodium metal, etc. maybe harvested and employed for other purposes, as desired. In someembodiments, described further below, HCl is a byproduct of the processand may be used, e.g. in the manufacture of poly (vinyl chloride) (PVC).

Methods of the invention include contacting a volume of an aqueoussolution of divalent cations with a source of CO₂ (to dissolve CO₂) andsubjecting the resultant solution to precipitation conditions. In someembodiments, a volume of an aqueous solution of divalent cations iscontacted with a source of CO₂ (to dissolve CO₂) while subjecting theaqueous solution to precipitation conditions. The dissolution of CO₂into the aqueous solution of divalent cations produces carbonic acid, aspecies in equilibrium with both bicarbonate and carbonate. In order toproduce carbonate-containing precipitation material, protons are removedfrom various species (e.g. carbonic acid, bicarbonate, hydronium, etc.)in the divalent cation-containing solution to shift the equilibriumtoward carbonate. As protons are removed, more CO₂ goes into solution.In some embodiments, proton-removing agents and/or methods are usedwhile contacting a divalent cation-containing aqueous solution with CO₂to increase CO₂ absorption in one phase of the precipitation reaction,wherein the pH may remain constant, increase, or even decrease, followedby a rapid removal of protons (e.g., by addition of a base) to causerapid precipitation of carbonate-containing precipitation material.Protons may be removed from the various species (e.g. carbonic acid,bicarbonate, hydronium, etc.) by any convenient approach, including, butnot limited to use of naturally occurring proton-removing agents, use ofmicroorganisms and fungi, use of synthetic chemical proton-removingagents, recovery of man-made waste streams, and using electrochemicalmeans.

Naturally occurring proton-removing agents encompass any proton-removingagents that can be found in the wider environment that may create orhave a basic local environment. Some embodiments provide for naturallyoccurring proton-removing agents including minerals that create basicenvironments upon addition to solution. Such minerals include, but arenot limited to, lime (CaO); periclase (MgO); iron hydroxide minerals(e.g., goethite and limonite); and volcanic ash. Methods for digestionof such minerals and rocks comprising such minerals are provided herein.Some embodiments provide for using naturally alkaline bodies of water asnaturally occurring proton-removing agents. Examples of naturallyalkaline bodies of water include, but are not limited to surface watersources (e.g. alkaline lakes such as Mono Lake in California) and groundwater sources (e.g. basic aquifers such as the deep geologic alkalineaquifers located at Searles Lake in California). Other embodimentsprovide for use of deposits from dried alkaline bodies of water such asthe crust along Lake Natron in Africa's Great Rift Valley. In someembodiments, organisms that excrete basic molecules or solutions intheir normal metabolism are used as proton-removing agents. Examples ofsuch organisms are fungi that produce alkaline protease (e.g., thedeep-sea fungus Aspergillus ustus with an optimal pH of 9) and bacteriathat create alkaline molecules (e.g., cyanobacteria such as Lyngbya sp.from the Atlin wetland in British Columbia, which increases pH from abyproduct of photosynthesis). In some embodiments, organisms are used toproduce proton-removing agents, wherein the organisms (e.g., Bacilluspasteurii, which hydrolyzes urea to ammonia) metabolize a contaminant(e.g. urea) to produce proton-removing agents or solutions comprisingproton-removing agents (e.g., ammonia, ammonium hydroxide). In someembodiments, organisms are cultured separately from the precipitationreaction mixture, wherein proton-removing agents or solution comprisingproton-removing agents are used for addition to the precipitationreaction mixture. In some embodiments, naturally occurring ormanufactured enzymes are used in combination with proton-removing agentsto invoke precipitation of precipitation material. Carbonic anhydrase,which is an enzyme produced by plants and animals, acceleratestransformation of carbonic acid to bicarbonate in aqueous solution.

Chemical agents for effecting proton removal generally refer tosynthetic chemical agents that are produced in large quantities and arecommercially available. For example, chemical agents for removingprotons include, but are not limited to, hydroxides, organic bases,super bases, oxides, ammonia, and carbonates. Hydroxides includechemical species that provide hydroxide anions in solution, including,for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), calciumhydroxide (Ca(OH)₂), or magnesium hydroxide (Mg(OH)₂). Organic bases arecarbon-containing molecules that are generally nitrogenous basesincluding primary amines such as methyl amine, secondary amines such asdiisopropylamine, tertiary such as diisopropylethylamine, aromaticamines such as aniline, heteroaromatics such as pyridine, imidazole, andbenzimidazole, and various forms thereof. In some embodiments, anorganic base selected from pyridine, methylamine, imidazole,benzimidazole, histidine, and a phophazene is used to remove protonsfrom various species (e.g., carbonic acid, bicarbonate, hydronium, etc.)for precipitation of precipitation material. In some embodiments,ammonia is used to raise pH to a level sufficient to precipitateprecipitation material from a solution of divalent cations and anindustrial waste stream. Super bases suitable for use as proton-removingagents include sodium ethoxide, sodium amide (NaNH₂), sodium hydride(NaH), butyl lithium, lithium diisopropylamide, lithium diethylamide,and lithium bis(trimethylsilyl)amide. Oxides including, for example,calcium oxide (CaO), magnesium oxide (MgO), strontium oxide (SrO),beryllium oxide (BeO), and barium oxide (BaO) are also suitableproton-removing agents that may be used. Carbonates for use in theinvention include, but are not limited to, sodium carbonate.

In addition to comprising cations of interest and other suitable metalforms, waste streams from various industrial processes may provideproton-removing agents. Such waste streams include, but are not limitedto, mining wastes; fossil fuel burning ash (e.g., combustion ash such asfly ash, bottom ash, boiler slag); slag (e.g. iron slag, phosphorousslag); cement kiln waste; oil refinery/petrochemical refinery waste(e.g. oil field and methane seam brines); coal seam wastes (e.g. gasproduction brines and coal seam brine); paper processing waste; watersoftening waste brine (e.g., ion exchange effluent); silicon processingwastes; agricultural waste; metal finishing waste; high pH textilewaste; and caustic sludge. Mining wastes include any wastes from theextraction of metal or another precious or useful mineral from theearth. In some embodiments, wastes from mining are used to modify pH,wherein the waste is selected from red mud from the Bayer aluminumextraction process; waste from magnesium extraction from sea water(e.g., Mg(OH)₂ such as that found in Moss Landing, Calif.); and wastesfrom mining processes involving leaching. For example, red mud may beused to modify pH as described in U.S. Provisional Patent ApplicationNo. 61/161,369, titled, “NEUTRALIZING INDUSTRIAL WASTES UTILIZING CO₂AND A DIVALENT CATION SOLUTION”, filed 18 Mar. 2009, which is herebyincorporated by reference in its entirety. Fossil fuel burning ash,cement kiln dust, and slag, collectively waste sources of metal oxides,further described in U.S. patent application Ser. No. 12/486,692,titled, “METHODS AND SYSTEMS FOR UTILIZING WASTE SOURCES OF METALOXIDES,” filed 17 Jun. 2009, the disclosure of which is incorporatedherein in its entirety, may be used in alone or in combination withother proton-removing agents to provide proton-removing agents for theinvention. Agricultural waste, either through animal waste or excessivefertilizer use, may contain potassium hydroxide (KOH) or ammonia (NH₃)or both. As such, agricultural waste may be used in some embodiments ofthe invention as a proton-removing agent. This agricultural waste isoften collected in ponds, but it may also percolate down into aquifers,where it can be accessed and used.

Electrochemical methods are another means to remove protons from variousspecies in a solution, either by removing protons from solute (e.g.,deprotonation of carbonic acid or bicarbonate) or from solvent (e.g.,deprotonation of hydronium or water). Deprotonation of solvent mayresult, for example, if proton production from CO₂ dissolution matchesor exceeds electrochemical proton removal from solute molecules. In someembodiments, low-voltage electrochemical methods are used to removeprotons, for example, as CO₂ is dissolved in the precipitation reactionmixture or a precursor solution to the precipitation reaction mixture(i.e., a solution that may or may not contain divalent cations). In someembodiments, CO₂ dissolved in an aqueous solution that does not containdivalent cations is treated by a low-voltage electrochemical method toremove protons from carbonic acid, bicarbonate, hydronium, or anyspecies or combination thereof resulting from the dissolution of CO₂. Alow-voltage electrochemical method operates at an average voltage of 2,1.9, 1.8, 1.7, or 1.6 V or less, such as 1.5, 1.4, 1.3, 1.2, 1.1 V orless, such as 1 V or less, such as 0.9 V or less, 0.8 V or less, 0.7 Vor less, 0.6 V or less, 0.5 V or less, 0.4 V or less, 0.3 V or less, 0.2V or less, or 0.1 V or less. Low-voltage electrochemical methods that donot generate chlorine gas are convenient for use in systems and methodsof the invention. Low-voltage electrochemical methods to remove protonsthat do not generate oxygen gas are also convenient for use in systemsand methods of the invention. In some embodiments, low-voltageelectrochemical methods generate hydrogen gas at the cathode andtransport it to the anode where the hydrogen gas is converted toprotons. Electrochemical methods that do not generate hydrogen gas mayalso be convenient. In some embodiments, electrochemical processes toremove protons do not generate a gas at the anode. In some instances,electrochemical methods to remove protons do not generate any gaseousby-byproduct. Electrochemical methods for effecting proton removal arefurther described in U.S. patent application Ser. No. 12/344,019,titled, “METHODS OF SEQUESTERING CO₂,” filed 24 Dec. 2008; U.S. patentapplication Ser. No. 12/375,632, titled, “LOW ENERGY ELECTROCHEMICALHYDROXIDE SYSTEM AND METHOD,” filed 23 Dec. 2008; International PatentApplication No. PCT/US08/088,242, titled, “LOW ENERGY ELECTROMECHANICALHYDROXIDE SYSTEM AND METHOD,” filed 23 Dec. 2008; International PatentApplication No. PCT/US09/32301, titled, “LOW-ENERGY ELECTROCHEMICALBICARBONATE ION SOLUTION,” filed 28 Jan. 2009; and International PatentApplication No. PCT/US09/48511, titled, “LOW-ENERGY 4-CELLELECTROCHEMICAL SYSTEM WITH CARBON DIOXIDE GAS,” filed 24 Jun. 2009,each of which are incorporated herein by reference in their entirety.

Low voltage electrochemical processes may produce hydroxide at thecathode and protons at the anode; where such processes utilize a saltcontaining chloride, e.g. NaCl, a product of the process will be HCl. Insome embodiments of the invention, the HCL from a low-voltageelectrochemical process as described herein may be used to makepoly(vinyl chloride) (PVC). HCl from a low-voltage electrochemicalprocess, e.g. a process that operates at a voltage of less than 2.0V, orless than 1.5V, or less than 1.0V, may be used in reactions well-knownin the art to produce a vinyl chloride monomer. The vinyl chloridemonomer may be used to produce poly(vinyl chloride) in some embodiments.In further embodiments, the PVC can be mixed with a carbonateprecipitate formed by the methods described herein, e.g. a slightly wetcarbonate precipitate, to form a building material. In some embodiments,the PVC/carbonate mixture may be extruded to form a slightly foamedprofile, such as, e.g. a 2×4 or other lumber material. Carbonate/PVClumber formed by such methods are thus encompassed by the invention.Such 1 umber may be CO₂-sequestering because the carbonate in the lumberis a CO₂-sequestering additive. In some embodiments, the amount of CO₂sequestering additive in the formed element comprising PVC is 5 wt % ormore. In some embodiments, the amount of CO₂ sequestering additive inthe formed element comprising PVC is 10 wt % or more, 15 wt % or more,20 wt % or more, 25 wt % or more, 30 wt % or more, 35 wt % or more, suchas 40 wt % or more, 45 wt % or more, 50 wt %, 55 wt % or more, 60 wt %or more, such as up to 65 wt % or more. In some embodiments, the amountof CO₂ sequestering additive in the formed element comprising PVC is 60wt % or more. In some embodiments, the PVC and CO₂ sequestering additiveare mixed and formed in a screw extruder. In some embodiments, theformed element is injection molded. In some embodiments, the PVC isfoamed to create a cellular structure that will hold anchoring devicessuch as nails and screws. In some embodiments, the formed elementcomprising PVC and CO₂ sequestering additive is used to fabricatebuilding elements that are flame resistant. In some embodiments, theformed element comprising PVC and CO₂ sequestering additive is such thatthe amount of CO₂ sequestering additive increases the finishability,i.e. ease of cutting and sanding, of the formed element. In someembodiments, the formed element comprising PVC and CO₂ sequesteringadditive is such that the amount of CO₂ sequestering additive enhancesthe coloring or appearance of the formed element. In some embodiments,the formed element comprising PVC and CO₂ sequestering additive is suchthat the amount of CO₂ sequestering additive gives stiffness to theformed element. In some embodiments, the CO₂ sequestering additive isadded to the PVC during the production of the PVC. In some suchembodiments, the PVC can be derived from the CO₂ sequestering methods ofthe invention.

Alternatively, electrochemical methods may be used to produce causticmolecules (e.g., hydroxide) through, for example, the chlor-alkaliprocess, or modification thereof. Electrodes (i.e., cathodes and anodes)may be present in the apparatus containing the divalentcation-containing aqueous solution or gaseous waste stream-charged(e.g., CO₂-charged) solution, and a selective barrier, such as amembrane, may separate the electrodes. Electrochemical systems andmethods for removing protons may produce by-products (e.g., hydrogen)that may be harvested and used for other purposes. Additionalelectrochemical approaches that may be used in systems and methods ofthe invention include, but are not limited to, those described in U.S.patent application Ser. No. 12/503,557, titled, “CO₂ UTILIZATION INELECTROCHEMICAL SYSTEMS,” filed 15 Jul. 2009 and U.S. ProvisionalApplication No. 61/091,729, titled, “LOW ENERGY ABSORPTION OF HYDROGENION FROM AN ELECTROLYTE SOLUTION INTO A SOLID MATERIAL,” filed 11 Sep.2008, the disclosures of which are herein incorporated by reference.

Combinations of the above mentioned sources of proton removal may beemployed. One such combination is the use of a microorganisms andelectrochemical systems. Combinations of microorganisms andelectrochemical systems include microbial electrolysis cells, includingmicrobial fuel cells, and bio-electrochemically assisted microbialreactors. In such microbial electrochemical systems, microorganisms(e.g. bacteria) are grown on or very near an electrode and in the courseof the metabolism of material (e.g. organic material) electrons aregenerated that are taken up by the electrode.

Additives other than pH elevating agents may also be introduced into thewater in order to influence the nature of the precipitate that isproduced. As such, certain embodiments of the methods include providingan additive in water before or during the time when the water issubjected to the precipitation conditions. Certain calcium carbonatepolymorphs can be favored by trace amounts of certain additives. Forexample, vaterite, a highly unstable polymorph of CaCO₃ whichprecipitates in a variety of different morphologies and converts rapidlyto calcite, can be obtained at very high yields by including traceamounts of lanthanum as lanthanum chloride in a supersaturated solutionof calcium carbonate. Other additives beside lanthanum that are ofinterest include, but are not limited to transition metals and the like.For instance, the addition of ferrous or ferric iron is known to favorthe formation of disordered dolomite (protodolomite) where it would notform otherwise.

The nature of the precipitate can also be influenced by selection ofappropriate major ion ratios. Major ion ratios also have considerableinfluence of polymorph formation. For example, as the magnesium:calciumratio in the water increases, aragonite becomes the favored polymorph ofcalcium carbonate over low-magnesium calcite. At low magnesium:calciumratios, low-magnesium calcite is the preferred polymorph. As such, awide range of magnesium:calcium ratios can be employed, including, e.g.,100/1, 50/1, 20/1, 10/1, 5/1, 2/1, 1/1, 1/2, 1/5, 1/10, 1/20, 1/50,1/100. In certain embodiments, the magnesium:calcium ratio is determinedby the source of water employed in the precipitation process (e.g.,seawater, brine, brackish water, fresh water), whereas in otherembodiments, the magnesium:calcium ratio is adjusted to fall within acertain range.

Rate of precipitation also has a large effect on compound phaseformation. The most rapid precipitation can be achieved by seeding thesolution with a desired phase. Without seeding, rapid precipitation canbe achieved by rapidly increasing the pH of the sea water, which resultsin more amorphous constituents. When silica is present, the more rapidthe reaction rate, the more silica is incorporated with the carbonateprecipitate. The higher the pH is, the more rapid the precipitation isand the more amorphous the precipitate is.

Accordingly, a set of precipitation conditions to produce a desiredprecipitate from a water include, in certain embodiments, the water'stemperature and pH, and in some instances the concentrations ofadditives and ionic species in the water. Precipitation conditions mayalso include factors such as mixing rate, forms of agitation such asultrasonics, and the presence of seed crystals, catalysts, membranes, orsubstrates. In some embodiments, precipitation conditions includesupersaturated conditions, temperature, pH, and/or concentrationgradients, or cycling or changing any of these parameters. The protocolsemployed to prepare carbonate compound precipitates according to theinvention may be batch or continuous protocols. It will be appreciatedthat precipitation conditions may be different to produce a givenprecipitate in a continuous flow system compared to a batch system.

In certain embodiments, the methods further include contacting thevolume of water that is subjected to the mineral precipitationconditions with a source of CO₂. Contact of the water with the sourceCO₂ may occur before and/or during the time when the water is subjectedto CO₂ precipitation conditions. Accordingly, embodiments of theinvention include methods in which the volume of water is contacted witha source of CO₂ prior to subjecting the volume of saltwater to mineralprecipitation conditions. Embodiments of the invention include methodsin which the volume of salt water is contacted with a source of CO₂while the volume of saltwater is being subjected to carbonate compoundprecipitation conditions. Embodiments of the invention include methodsin which the volume of water is contacted with a source of a CO₂ bothprior to subjecting the volume of saltwater to carbonate compoundprecipitation conditions and while the volume of saltwater is beingsubjected to carbonate compound precipitation conditions. In someembodiments, the same water may be cycled more than once, wherein afirst cycle of precipitation removes primarily calcium carbonate andmagnesium carbonate minerals, and leaves remaining alkaline water towhich other alkaline earth ion sources may be added, that can have morecarbon dioxide cycled through it, precipitating more carbonatecompounds.

The source of CO₂ that is contacted with the volume of saltwater inthese embodiments may be any convenient CO₂ source. The CO₂ source maybe a liquid, solid (e.g., dry ice) or gaseous CO₂ source. In certainembodiments, the CO₂ source is a gaseous CO₂ source. This gaseous CO₂is, in certain instances, a waste feed from an industrial plant. Thenature of the industrial plant may vary in these embodiments, whereindustrial plants of interest include power plants (e.g., as describedin further detail in International Application No. PCT/US08/88318,titled, “METHODS OF SEQUESTERING CO₂,” filed 24 Dec. 2008, thedisclosure of which is herein incorporated by reference), chemicalprocessing plants, steel mills, paper mills, cement plants (e.g., asdescribed in further detail in U.S. Provisional Application Ser. No.61/088,340, the disclosure of which is herein incorporated byreference), and other industrial plants that produce CO₂ as a byproduct.By waste feed is meant a stream of gas (or analogous stream) that isproduced as a byproduct of an active process of the industrial plant.The gaseous stream may be substantially pure CO₂ or a multi-componentgaseous stream that includes CO₂ and one or more additional gases.Multi-component gaseous streams (containing CO₂) that may be employed asa CO₂ source in embodiments of the subject methods include bothreducing, e.g., syngas, shifted syngas, natural gas, and hydrogen andthe like, and oxidizing condition streams, e.g., flue gases fromcombustion. Exhaust gases containing NOx, SOx, VOCs, particulates and Hgwould commonly incorporate these compounds along with the carbonate inthe precipitated product. Particular multi-component gaseous streams ofinterest that may be treated according to the subject invention include:oxygen containing combustion power plant flue gas, turbo charged boilerproduct gas, coal gasification product gas, shifted coal gasificationproduct gas, anaerobic digester product gas, wellhead natural gasstream, reformed natural gas or methane hydrates, and the like.

The volume of saltwater may be contacted with the CO₂ source using anyconvenient protocol. Where the CO₂ is a gas, contact protocols ofinterest include, but are not limited to: direct contacting protocols,e.g., bubbling the gas through the volume of saltwater, concurrentcontacting means, i.e., contact between unidirectionally flowing gaseousand liquid phase streams, countercurrent means, i.e., contact betweenoppositely flowing gaseous and liquid phase streams, and the like. Thus,contact may be accomplished through use of infusers, bubblers, fluidicVenturi reactor, sparger, gas filter, spray, tray, or packed columnreactors, and the like, as may be convenient.

The above protocol results in the production of a slurry of a CO₂sequestering precipitate and a mother liquor. Where desired, thecompositions made up of the precipitate and the mother liquor may bestored for a period of time following precipitation and prior to furtherprocessing. For example, the composition may be stored for a period oftime ranging from 1 to 1000 days or longer, such as 1 to 10 days orlonger, at a temperature ranging from 1 to 40° C., such as 20 to 25° C.

The slurry components are then separated. Embodiments may includetreatment of the mother liquor, where the mother liquor may or may notbe present in the same composition as the product. For example, wherethe mother liquor is to be returned to the ocean, the mother liquor maybe contacted with a gaseous source of CO₂ in a manner sufficient toincrease the concentration of carbonate ion present in the motherliquor. Contact may be conducted using any convenient protocol, such asthose described above. In certain embodiments, the mother liquor has analkaline pH, and contact with the CO₂ source is carried out in a mannersufficient to reduce the pH to a range between 5 and 9, e.g., 6 and 8.5,including 7.5 to 8.2. In certain embodiments, the treated brine may becontacted with a source of CO₂, e.g., as described above, to sequesterfurther CO₂. For example, where the mother liquor is to be returned tothe ocean, the mother liquor may be contacted with a gaseous source ofCO₂ in a manner sufficient to increase the concentration of carbonateion present in the mother liquor. Contact may be conducted using anyconvenient protocol, such as those described above. In certainembodiments, the mother liquor has an alkaline pH, and contact with theCO₂ source is carried out in a manner sufficient to reduce the pH to arange between 5 and 9, e.g., 6 and 8.5, including 7.5 to 8.2.

The resultant mother liquor of the reaction may be disposed of using anyconvenient protocol. In certain embodiments, it may be sent to atailings pond for disposal. In certain embodiments, it may be disposedof in a naturally occurring body of water, e.g., ocean, sea, lake orriver. In certain embodiments, the mother liquor is returned to thesource of feedwater for the methods of invention, e.g., an ocean or sea.Alternatively, the mother liquor may be further processed, e.g.,subjected to desalination protocols, as described further in U.S.application Ser. No. 12/163,205; the disclosure of which is hereinincorporated by reference.

In certain embodiments, following production of the CO₂ sequesteringproduct, the resultant product is separated from the mother liquor toproduce separated CO₂ sequestering product. Separation of the productcan be achieved using any convenient approach, including a mechanicalapproach, e.g., where bulk excess water is drained from the product,e.g., either by gravity alone or with the addition of vacuum, mechanicalpressing, by filtering the product from the mother liquor to produce afiltrate, etc. Separation of bulk water produces, in certainembodiments, a wet, dewatered precipitate.

The resultant dewatered precipitate may then be dried, as desired, toproduce a dried product. Drying can be achieved by air drying the wetprecipitate. Where the wet precipitate is air dried, air drying may beat room or elevated temperature. In yet another embodiment, the wetprecipitate is spray dried to dry the precipitate, where the liquidcontaining the precipitate is dried by feeding it through a hot gas(such as the gaseous waste stream from the power plant), e.g., where theliquid feed is pumped through an atomizer into a main drying chamber anda hot gas is passed as a co-current or counter-current to the atomizerdirection. Depending on the particular drying protocol of the system,the drying station may include a filtration element, freeze dryingstructure, spray drying structure, etc. Where desired, the dewateredprecipitate product may be washed before drying. The precipitate may bewashed with freshwater, e.g., to remove salts (such as NaCl) from thedewatered precipitate.

In certain embodiments, the precipitate product is refined (i.e.,processed) in some manner prior to subsequent use. Refinement mayinclude a variety of different protocols. In certain embodiments, theproduct is subjected to mechanical refinement, e.g., grinding, in orderto obtain a product with desired physical properties, e.g., particlesize, etc.

FIG. 1 provides a schematic flow diagram of a process for producing aCO₂ sequestering product according to an embodiment of the invention. InFIG. 1, saltwater from salt water source 10 is subjected to carbonatecompound precipitation conditions at precipitation step 20. As reviewedabove, term “saltwater” is employed in its conventional sense to refer anumber of different types of aqueous fluids other than fresh water,where the term “saltwater” includes brackish water, sea water and brine(including man-made brines, e.g., geothermal plant wastewaters,desalination waste waters, etc), as well as other salines having asalinity that is greater than that of freshwater. The saltwater sourcefrom which the carbonate compound composition of the cements of theinvention is derived may be a naturally occurring source, such as a sea,ocean, lake, swamp, estuary, lagoon, etc., or a man-made source.

In certain embodiments, the water may be obtained from the power plantthat is also providing the gaseous waste stream. For example, in watercooled power plants, such as seawater cooled power plants, water thathas been employed by the power plant may then be sent to theprecipitation system and employed as the water in the precipitationreaction. In certain of these embodiments, the water may be cooled priorto entering the precipitation reactor.

In the embodiment depicted in FIG. 1, the water from saltwater source 10is first charged with CO₂ to produce CO₂ charged water, which CO₂ isthen subjected to carbonate compound precipitation conditions. Asdepicted in FIG. 1, a CO₂ gaseous stream 30 is contacted with the waterat precipitation step 20. The provided gaseous stream 30 is contactedwith a suitable water at precipitation step 20 to produce a CO₂ chargedwater. By CO₂ charged water is meant water that has had CO₂ gascontacted with it, where CO₂ molecules have combined with watermolecules to produce, e.g., carbonic acid, bicarbonate and carbonateion. Charging water in this step results in an increase in the “CO₂content” of the water, e.g., in the form of carbonic acid, bicarbonateand carbonate ion, and a concomitant decrease in the pCO₂ of the wastestream that is contacted with the water. The CO₂ charged water isacidic, having a pH of 6 or less, such as 5 or less and including 4 orless. In certain embodiments, the concentration of CO₂ of the gas thatis used to charge the water is 10% or higher, 25% or higher, including50% or higher, such as 75% or even higher. Contact protocols of interestinclude, but are not limited to: direct contacting protocols, e.g.,bubbling the gas through the volume of water, concurrent contactingmeans, i.e., contact between unidirectionally flowing gaseous and liquidphase streams, countercurrent means, i.e., contact between oppositelyflowing gaseous and liquid phase streams, and the like. Thus, contactmay be accomplished through use of infusers, bubblers, fluidic Venturireactor, sparger, gas filter, spray, tray, or packed column reactors,and the like, as may be convenient.

At precipitation step 20, carbonate compounds, which may be amorphous orcrystalline, are precipitated. Precipitation conditions of interestinclude those that change the physical environment of the water toproduce the desired precipitate product. For example, the temperature ofthe water may be raised to an amount suitable for precipitation of thedesired carbonate compound(s) to occur. In such embodiments, thetemperature of the water may be raised to a value from 5 to 70° C., suchas from 20 to 50° C. and including from 25 to 45° C. As such, while agiven set of precipitation conditions may have a temperature rangingfrom 0 to 100° C., the temperature may be raised in certain embodimentsto produce the desired precipitate. In certain embodiments, thetemperature is raised using energy generated from low or zero carbondioxide emission sources, e.g., solar energy source, wind energy source,hydroelectric energy source, etc. While the pH of the water may rangefrom 7 to 14 during a given precipitation process, in certainembodiments the pH is raised to alkaline levels in order to drive theprecipitation of carbonate compound as desired. In certain of theseembodiments, the pH is raised to a level which minimizes if noteliminates CO₂ gas generation production during precipitation. In theseembodiments, the pH may be raised to 10 or higher, such as 11 or higher.Where desired, the pH of the water is raised using any convenientapproach. In certain embodiments, a pH raising agent may be employed,where examples of such agents include oxides, hydroxides (e.g., sodiumhydroxide, potassium hydroxide, brucite), carbonates (e.g. sodiumcarbonate) and the like. The amount of pH elevating agent that is addedto the saltwater source will depend on the particular nature of theagent and the volume of saltwater being modified, and will be sufficientto raise the pH of the salt water source to the desired value.Alternatively, the pH of the saltwater source can be raised to thedesired level by electrolysis of the water.

CO₂ charging and carbonate compound precipitation may occur in acontinuous process or at separate steps. As such, charging andprecipitation may occur in the same reactor of a system, e.g., asillustrated in FIG. 1 at step 20, according to certain embodiments ofthe invention. In yet other embodiments of the invention, these twosteps may occur in separate reactors, such that the water is firstcharged with CO₂ in a charging reactor and the resultant CO₂ chargedwater is then subjected to precipitation conditions in a separatereactor.

Following production of the carbonate precipitate from the water, theresultant precipitated carbonate compound composition is separated fromthe mother liquor to produce separated carbonate compound precipitateproduct, as illustrated at step 40 of FIG. 1. Separation of theprecipitate can be achieved using any convenient approach, including amechanical approach, e.g., where bulk excess water is drained from theprecipitated, e.g., either by gravity alone or with the addition ofvacuum, mechanical pressing, by filtering the precipitate from themother liquor to produce a filtrate, etc. Separation of bulk waterproduces a wet, dewatered precipitate.

The resultant dewatered precipitate is then dried to produce a product,as illustrated at step 60 of FIG. 1. Drying can be achieved by airdrying the filtrate. Where the filtrate is air dried, air drying may beat room or elevated temperature. In yet another embodiment, theprecipitate is spray dried to dry the precipitate, where the liquidcontaining the precipitate is dried by feeding it through a hot gas(such as the gaseous waste stream from the power plant), e.g., where theliquid feed is pumped through an atomizer into a main drying chamber anda hot gas is passed as a co-current or counter-current to the atomizerdirection. Depending on the particular drying protocol of the system,the drying station may include a filtration element, freeze dryingstructure, spray drying structure, etc.

Where desired, the dewatered precipitate product from the separationreactor 40 may be washed before drying, as illustrated at optional step50 of FIG. 1. The precipitate may be washed with freshwater, e.g., toremove salts (such as NaCl) from the dewatered precipitate. Used washwater may be disposed of as convenient, e.g., by disposing of it in atailings pond, etc.

At step 70, the dried precipitate is refined, e.g., to provide fordesired physical characteristics, such as particle size, surface area,etc., or to add one or more components to the precipitate, such asadmixtures, aggregate, supplementary cementitious materials, etc., toproduce a final product 80.

In certain embodiments, a system is employed to perform the abovemethods.

Following production of the CO₂ sequestering component, e.g., asdescribed above, the CO₂ sequestering is then employed to produce anon-cementitious composition of the invention, e.g., as described above.

Utility

Compositions of the invention find use in a variety of differentapplications, as reviewed above. The subject methods and systems finduse in CO₂ sequestration, particularly via sequestration in a variety ofdiverse man-made products. By “sequestering CO₂” is meant the removal orsegregation of CO₂ from a gaseous stream, such as a gaseous wastestream, and fixating it into a stable non-gaseous form so that the CO₂cannot escape into the atmosphere. By “CO₂ sequestration” is meant theplacement of CO₂ into a storage stable form, where the CO₂ is fixed atleast during the useful life of the composition. As such, sequesteringof CO₂ according to methods of the invention results in prevention ofCO₂ gas from entering the atmosphere and long term storage of CO₂ in amanner that CO₂ does not become part of the atmosphere.

While preferred embodiments of the present invention have been shown anddescribed herein, it will be obvious to those skilled in the art thatsuch embodiments are provided by way of example only. Numerousvariations, changes, and substitutions will now occur to those skilledin the art without departing from the invention. It should be understoodthat various alternatives to the embodiments of the invention describedherein may be employed in practicing the invention. It is intended thatthe following claims define the scope of the invention and that methodsand structures within the scope of these claims and their equivalents becovered thereby.

1. A method of sequestering carbon dioxide, the method comprising:precipitating a CO₂ sequestering carbonate compound composition from analkaline-earth-metal-containing water, wherein the carbonate compoundcomposition comprises carbon that was released in the form of CO₂ fromthe combustion of fuel; and producing a CO₂ sequestering additivecomprising the carbonate compound composition; and producing anon-cementitious composition comprising the CO₂ sequestering additive.2. The method according to claim 1, wherein thealkaline-earth-metal-containing water is contacted to an industrialwaste stream prior to the precipitating step.